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.

Modeling the unidentified infrared emission with combinations of polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

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

1999-01-01

The infrared emission band spectrum associated with many different interstellar objects can be modeled successfully by using combined laboratory spectra of neutral and positively charged polycyclic aromatic hydrocarbons (PAHs). These model spectra, shown here for the first time, alleviate the principal spectroscopic criticisms previously leveled at the PAH hypothesis and demonstrate that mixtures of free molecular PAHs can indeed account for the overall appearance of the widespread interstellar infrared emission spectrum. Furthermore, these models give us insight into the structures, stabilities, abundances, and ionization balance of the interstellar PAH population. These, in turn, reflect conditions in the emission zones and shed light on the microscopic processes involved in the carbon nucleation, growth, and evolution in circumstellar shells and the interstellar medium.

Photochemistry of PAHs in cosmic water ice. The effect of concentration on UV-VIS spectroscopy and ionization efficiency

NASA Astrophysics Data System (ADS)

Cuylle, Steven H.; Allamandola, Louis J.; Linnartz, Harold

2014-02-01

Context. Observations and models show that polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the interstellar medium. Like other molecules in dense clouds, PAHs accrete onto interstellar dust grains, where they are embedded in an ice matrix dominated by water. In the laboratory, mixed molecular ices (not containing PAHs) have been extensively studied using Fourier transform infrared absorption spectroscopy. Experiments including PAHs in ices have started, however, the concentrations used are typically much higher than the concentrations expected for interstellar ices. Optical spectroscopy offers a sensitive alternative. Aims: We report an experimental study of the effect PAH concentration has on the electronic spectra and the vacuum UV (VUV) driven processes of PAHs in water-rich ices. The goal is to apply the outcome to cosmic ices. Methods: Optical spectroscopic studies allow us to obtain in-situ and quasi real-time electronic solid state spectra of two prototypical PAHs (pyrene and coronene) embedded in water ice under VUV photoprocessing. The study is carried out on PAH:H2O concentrations in the range of 1:30 000 to pure PAH, covering the temperature range from 12 to 125 K. Results: PAH concentration strongly influences the efficiency of PAH cation formation. At low concentrations, ionization efficiencies are over 60% dropping to about 15% at 1:1000. Increasing the PAH concentration reveals spectral broadening in neutral and cation PAH spectra attributed to PAH clustering inside the ice. At the PAH concentrations expected for interstellar ices, some 10 to 20% may be present as cations. The presence of PAHs in neutral and ion form will add distinctive absorption bands to cosmic ice optical spectra and this may serve as a tool to determine PAH concentrations.

Observational aspects of polycyclic aromatic hydrocarbon charging in the Interstellar Medium

NASA Technical Reports Server (NTRS)

Bakes, E. L. O.; Tielens, Alexander G. G. M.

1995-01-01

We have investigated the charging processes which affect small carbonaceous dust grains and polycyclic aromatic hydrocarbons (PAH's). Because of their high abundance, interstellar PAH molecules can dominate the charge balance of the interstellar medium (ISM), which controls the heating and cooling interstellar gas and interstellar chemistry. We present the results of our model, which compare well with observations and suggest further applications to both laboratory measurements and data obtainable from the KAO.

Spectroscopy of neutral and ionized PAHs. From laboratory studies to astronomical observations

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 astrochemistry is to reproduce (in a realistic way) the physical conditions that are associated with the emission and 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. PAHs, neutrals and ions, are expanded through a pulsed discharge nozzle (PDN) and probed with high-sensitivity cavity ringdown spectroscopy (CRDS). These laboratory experiments provide unique information on the spectra of free, cold large carbon molecules and ions in the gas phase from the ultraviolet and visible range to the near-infrared range. 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. Preliminary conclusions from the comparison of the laboratory data with astronomical observations of interstellar and circumstellar environments will also be discussed.

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,...).

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.

ESO Diffuse Interstellar Bands Large Exploration Survey (EDIBLES) - Merging Observations and Laboratory Data

NASA Technical Reports Server (NTRS)

Salama, Farid

2016-01-01

The Diffuse Interstellar Bands (DIBs) are a set of 500 absorption bands that are detected in the spectra of stars with interstellar clouds in the line of sight. DIBs are found from the NUV to the NIR in the spectra of reddened stars spanning different interstellar environments in our local, and in other galaxies. DIB carriers are a significant part of the interstellar chemical inventory. They are stable and ubiquitous in a broad variety of environments and play a unique role in interstellar physics/chemistry. It has long been realized that the solving of the DIB problem requires a strong synergy between astronomical observations, laboratory astrophysics, and astrophysical modeling of line-of-sights. PAHs are among the molecular species that have been proposed as DIB carriers. We will present an assessment of the PAH-DIB model in view of the progress and the advances that have been achieved over the past years through a series of studies involving astronomical observations of DIBs, laboratory simulation of interstellar analogs for neutrals and ionized PAHs, theoretical calculations of PAH spectra and the modelization of diffuse and translucent interstellar clouds. We will present a summary of what has been learned from these complementary studies, the constraints that can now be derived for the PAHs as DIB carriers in the context of the PAH-DIB model and how these constraints can be applied to the EDIBLES project. 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. 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 facilities, MIS and COSmIC, that have been 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. MIS stands for Matrix Isolation Spectroscopy, a well-proven technique for isolating cold molecular species in inert solid environments. COSmIC stands for Cosmic Simulation Chamber. It combines a supersonic free jet expansion with discharge plasma and high-sensitivity cavity ringdown spectroscopy and time-of-flight mass spectrometry detection tools for the generation and the detection of cold, isolated gas-phase molecules and ions under experimental conditions that closely mimic 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.

The spacing of the interstellar 6.2 and 7.7 micron emission features as an indicator of polycyclic aromatic hydrocarbon size

NASA Technical Reports Server (NTRS)

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

1999-01-01

A database of astrophysically relevant, infrared spectral measurements on a wide variety of neutral as well as positively and negatively charged polycyclic aromatic hydrocarbons (PAHs), ranging in size from C10H8 through C48H20, is now available to extend the interstellar PAH model. Beyond simply indicating general characteristics of the carriers, this collection of data now makes it possible to conduct a more thorough interpretation of the details of the interstellar spectra and thereby derive deeper insights into the nature of the emitting material and conditions in the emission zones. This Letter is the first such implementation of this spectral database. The infrared spectra of PAH cations, the main PAH form in the most energetic emission zones, are usually dominated by a few strong features in the 1650-1100 cm-1 (6.1-9.1 microns) region that tend to cluster the vicinity of the interstellar emission bands at 1610 and 1320 cm-1 (6.2 and 7.6 microns), but with spacings typically somewhat less than that observed in the canonical interstellar spectrum. However, the spectra in the database show that this spacing increases steadily with molecular size. Extrapolation of this trend indicates that PAHs in the 50-80 carbon atom size range are entirely consistent with the observed interstellar spacing. Furthermore, the profile of the 1610 cm-1 (6.2 microns) interstellar band indicates that PAHs containing as few as 20 carbon atoms contribute to this feature.

The Spacing of the Interstellar 6.2 Microns and 7.7 Microns Emission Features as an Indicator of PAH Size

NASA Technical Reports Server (NTRS)

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

1998-01-01

A database of astrophysically relevant, infrared spectral measurements on a wide variety of neutral as well as positively and negatively charged polycyclic aromatic hydrocarbons ranging in size from C10H8 through C48H20 is now available to extend the interstellar PAH model. Beyond simply indicating general characteristics of the carriers, this collection of data now makes it possible to conduct a more thorough interpretation of the details of the interstellar spectra and thereby derive deeper insights into the nature of the emitting material and conditions in the emission zones. This paper is the first such implementation of this spectral database. The infrared spectra of PAH cations, the main PAH form in the most energetic emission zones, are usually dominated by a few strong features in the 1650 - 1100 per centimeter (6.1 - 9.1 microns) region which tend to cluster in the vicinity of the interstellar emission bands at 1610 per centimeter and 1320 per centimeter (6.2 and 7.6 microns) but with spacings typically somewhat less than that observed in the canonical interstellar spectrum. However, the spectra in the database show that this spacing increases steadily with molecular size. Extrapolation of this trend indicates that PAHS in the 50 to 80 carbon atom size range are entirely consistent with the observed interstellar spacing. Furthermore, the profile of the 1610 per centimeter (6.2 microns) interstellar band indicates that PAHS containing as few as 20 carbon atoms contribute to this feature.

Recombination Rates of Electrons with Interstellar PAH Molecules

NASA Technical Reports Server (NTRS)

Ballester, Jorge (Cartographer)

1996-01-01

The goal of this project is to develop a general model for the recombination of electrons with PAH molecules in an interstellar environment. The model is being developed such that it can be applied to a small number of families of PAHs without reference to specific molecular structures. Special attention will be focused on modeling the approximately circular compact PAHs in a way that only depends on the number of carbon atoms.

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.

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.

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.

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.

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.

Experimental Near Infrared Spectroscopy of Polycyclic Aromatic Hydrocarbons Between 0.7 to 2.5 microns

NASA Technical Reports Server (NTRS)

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

2005-01-01

The near infrared (NIR) spectra and absolute band strengths of 27 polycyclic aromatic hydrocarbon (PAH) cations and anions ranging in size from C14H10 to C50H22, are reported. The spectra from 0.7 to 2.5 microns (14,000 to 4000/cm) are presented for the fifteen PAHs ranging in size from C40H18 to C50H22 whereas the spectra of the remaining twelve span the narrower range from 0.7 to 1.1 microns (14,000 to 9000/cm). The spectra of all the ionized PAHs we have studied to date have strong, broad absorption bands in the NIR arising from electronic transitions. This work shows that ionized PAHs have significant absorption bands at longer wavelengths than predicted by the current astronomical models which consider PAHs in their treatment of the radiation balance of the interstellar medium. Two implications are 1)-ionized interstellar PAHs should add weak, broad band structure to the NIR portion of the interstellar extinction curve and 2)- UV poor radiation fields can pump the PAH emission bands provided ionized PAHs are present.

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.

Molecular Spectroscopy in Astrophysics: The Case of Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

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

2000-01-01

The role of molecular spectroscopy in astrophysics and astrochemistry is discussed in the context of the study of large, complex, carbon-bearing molecules, namely, Polycyclic Aromatic Hydrocarbons or PAHs. These molecular species are now thought to be widespread in the interstellar medium in their neutral and ionized forms. Identifying the carriers responsible for unidentified interstellar spectral bands will allow to derive important information on cosmic elemental abundances as well as information on the physical conditions (density, temperature) reigning in specific interstellar environments. These, in turn, are key elements for a correct understanding of the energetic mechanisms that govern the origin and the evolution of the interstellar medium. A multidisciplinary approach - combining astronomical observations with laboratory simulations and theoretical modeling - is required to address these complex issues. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices or seeded in a supersonic jet expansion, are discussed here and compared to the astronomical spectra of reddened, early type, stars. The electronic spectroscopy of PAHs in the ultraviolet, visible, and near-infrared domains is reviewed and an assessment of the potential contribution of PAHs to the interstellar extinction in the ultraviolet and in the visible is discussed.

Theoretical modeling of the infrared fluorescence from interstellar polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

Schutte, W. A.; Tielens, A. G. G. M.; Allamandola, L. J.

1993-01-01

We have modeled the family of interstellar IR emission bands at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 microns by calculating the fluorescence from a size distribution of interstellar polycyclic aromatic hydrocarbons (PAHs) embedded in the radiation field of a hot star. It is found that the various emission bands are dominated by distinctly different PAHs, from molecules with much less than about 80 C atoms for the 3.3 micron feature, to molecules with 10 exp 2-10 exp 5 C atoms for the emission in the IRAS 12 and 25 micron bands. We quantitatively describe the influence on the emergent spectrum of various PAH properties such as the molecular structure, the amount of dehydrogenation, the intrinsic strength of the IR active modes, and the size distribution. Comparing our model results to the emission spectrum from the Orion Bar region, we conclude that interstellar PAHs are likely fully, or almost fully, hydrogenated. Moreover, it is found that the intrinsic strengths of the 6.2 and 7.7 micron C-C stretching modes, and the 8.6 micron C-H in-plane bending mode are 2-6 times larger than measured for neutral PAHs in the laboratory.

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.

Carbon atom clusters in random covalent networks: PAHs as an integral component of interstellar HAC

NASA Astrophysics Data System (ADS)

Jones, A. P.

1990-11-01

Using a random covalent network (RCN) model for the structure of hydrogenated amorphorous carbon (HAC) and the available laboratory data, it is shown that aromatic species are a natural consequence of the structure of amorphous carbons formed in the laboratory. Amorphous carbons in the interstellar medium are therefore likely to contain a significant fraction of Polycyclic aromatic hydrocarbons (PAH) species within the 'amorphous' matrix making up these materials. This aromatic component can be produced in situ during the accretion of gas phase carbon species on to grains in the interstellar medium under hydrogen-poor conditions, or subsequent to deposition as a result of photolysis (photodarkening). The fraction of interstellar carbon present in HAC in the form of PAHs, based upon a RCN model, is consistent with the observed Unidentified infrared (UIR) emission features.

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.

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

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.

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.

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

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.

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.

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.

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).

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 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.

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.

ISO Mid-Infrared Spectra of Reflection Nebulae

NASA Technical Reports Server (NTRS)

Werner, M.; Uchida, K.; Sellgren, K.; Houdashelt, M.

1999-01-01

Our goal is to test predictions of models attributing the IEFs to polycyclic aromatic hydrocarbons (PAHs). Interstellar models predict PAHs change from singly ionized to neutral as the UV intensity, Go, decreases.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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

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.

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.

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.

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.

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.

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

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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

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

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Identification, characterization and quantitation of pyrogenic polycylic aromatic hydrocarbons and other organic compounds in tire fire products.

PubMed

Wang, Zhendi; Li, K; Lambert, P; Yang, Chun

2007-01-12

On 15 August 2001, a tire fire took place at the Pneu Lavoie Facility in Gatineau, Quebec, in which 4000 to 6000 new and recycled tires were stored along with other potentially hazardous materials. Comprehensive gas chromatography-mass spectrometry (GC-MS) analyses were performed on the tire fire samples to facilitate detailed chemical composition characterization of toxic polycyclic aromatic hydrocarbons (PAHs) and other organic compounds in samples. It is found that significant amounts of PAHs, particularly the high-ring-number PAHs, were generated during the fire. In total, 165 PAH compounds including 13 isomers of molecular weight (MW) 302, 10 isomers of MW 278, 10 isomers of MW 276, 7 isomers of MW 252, 7 isomers of MW 228, and 8 isomers of MW 216 PAHs were positively identified in the tire fire wipe samples for the first time. Numerous S-, O-, and N-containing PAH compounds were also detected. The identification and characterization of the PAH isomers was mainly based on: (1) a positive match of mass spectral data of the PAH isomers with the NIST authentic mass spectra database; (2) a positive match of the GC retention indices (I) of PAHs with authentic standards and with those reported in the literature; (3) agreement of the PAH elution order with the NIST (US National Institute of Standards and Technology) Standard Reference Material 1597 for complex mixture of PAHs from coal tar; (4) a positive match of the distribution patterns of PAH isomers in the SIM mode between the tire fire samples and the NIST Standard Reference Materials and well-characterized reference oils. Quantitation of target PAHs was done on the GC-MS in the selected ion monitoring (SIM) mode using the internal standard method. The relative response factors (RRF) for target PAHs were obtained from analyses of authentic PAH standard compounds. Alkylated PAH homologues were quantitated using straight baseline integration of each level of alkylation.

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

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.

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.

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.

Emission characterization and δ(13)C values of parent PAHs and nitro-PAHs in size-segregated particulate matters from coal-fired power plants.

PubMed

Wang, Ruwei; Yousaf, Balal; Sun, Ruoyu; Zhang, Hong; Zhang, Jiamei; Liu, Guijian

2016-11-15

The objective of this study was to characterize parent polycyclic aromatic hydrocarbons (pPAHs) and their nitrated derivatives (NPAHs) in coarse (PM2.5-10), intermediate (PM1-2.5) and fine (PM1) particulate matters emitted from coal-fired power plants (CFPPs) in Huainan, China. The diagnostic ratios and the stable carbon isotopic approaches to characterize individual PAHs were applied in order to develop robust tools for tracing the origins of PAHs in different size-segregated particular matters (PMs) emitted CFPP coal combustion. The concentrations of PAH compounds in flue gas emissions varied greatly, depending on boiler types, operation and air pollution control device (APCD) conditions. Both pPAHs and NPAHs were strongly enriched in PM1-2.5 and PM1. In contrary to low molecular weight (LMW) PAHs, high molecular weight (HMW) PAHs were more enriched in finer PMs. The PAH diagnostic ratios in size-segregated PMs are small at most cases, highlighting their potential application in tracing CFPP emitted PAHs attached to different sizes of PMs. Yet, substantial uncertainty still exists to directly apply PAH diagnostic ratios as emission tracers. Although the stable carbon isotopic composition of PAH molecular was useful in differentiating coal combustion emissions from other sources such as biomass combustion and vehicular exhausts, it was not feasible to differentiate isotopic fractionation processes such as low-temperature carbonization, high-temperature carbonization, gasification and combustion. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

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.

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.

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.

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.

Characterization of the ambient air content of parent polycyclic aromatic hydrocarbons in the Fort McKay region (Canada).

PubMed

Wnorowski, Andrzej

2017-05-01

This study presents the characterization of the gas-particle partition and size distribution of seven parent polycyclic aromatic hydrocarbons (PAHs) in ambient air samples collected in the proximity of oil sands exploration and compares their time-integrated concentration levels with nineteen analogous oxidation products - quinones. Gas-phase (GP) and particle-phase (PM) ambient air aerosol samples that were collected separately in summer for either 24 h or 12 h (day and night) revealed a higher PAH partition in the GP than in the PM, with the distribution over tenfold higher for light over heavy PAHs. Diurnal/nocturnal samples demonstrated that night conditions lead to lower concentrations, linking some of the sources of these compounds with daytime activity emissions. PAHs were observed to transform more efficiently in the GP, and quinone levels increased in the PM with time. Correlation data indicated that parent PAHs originated from primary emission sources associated with oil sand activities and that quinone formation paralleled a reduction in PAH levels. The findings of this study shed new light on characterization of PAHs in the Athabasca oil sands region. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

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

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.

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.

Physicochemical characterization of coke-plant soil for the assessment of polycyclic aromatic hydrocarbon availability and the feasibility of phytoremediation

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

Ahn, S.; Werner, D.; Luthy, R.G.

Coke oven site soil was characterized to assess the particle association and availability of polycyclic aromatic hydrocarbons (PAHs). We identified various carbonaceous materials including coal, coke, pitch, and tar decanter sludge. Most of the PAHs were associated with the polymeric matrix of tar sludge or hard pitch as discrete particles, coatings on soil mineral particles, or complex aggregates. The PAH availability from these particles was very low due to hindered diffusive release from solid tar or pitch with apparent diffusivities of 6 x 10{sup -15} for phenanthrene, 3 x 10{sup -15} for pyrene, and 1 x 10{sup -15} cm{sup 2}/smore » for benzo(a)pyrene. Significant concentrations of PAHs were observed in the interior of solid tar aggregates with up to 40,000 mg/kg total PAHs. The release of PAHs from the interior of such particles requires diffusion over a substantial distance, and semipermeable membrane device tests confirmed a very limited availability of PAHs. These findings explain the results from three years of phytoremediation of the site soil, for which no significant changes in the total PAH concentrations were observed in the test plot samples. The observed low bioavailability of PAHs probably inhibited PAH phytoremediation, as diffusion-limited mass transfer would limit the release of PAHs to the aqueous phase.« less

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).

Characterization and distribution of polycyclic aromatic hydrocarbon contaminations in surface sediment and water from Gao-ping River, Taiwan.

PubMed

Doong, Ruey-An; Lin, Yu-Tin

2004-04-01

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in water and sediment samples collected from 12 locations in Gao-ping River, Taiwan were analyzed. Molecular ratios and principal component analysis (PCA) were used to characterize the possible pollution sources. Concentrations of total 16 PAHs (SigmaPAHs) in water samples ranged from below method detection limits (

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.

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.

Identification and removal of polycyclic aromatic hydrocarbons in wastewater treatment processes from coke production plants.

PubMed

Zhang, Wanhui; Wei, Chaohai; Yan, Bo; Feng, Chunhua; Zhao, Guobao; Lin, Chong; Yuan, Mengyang; Wu, Chaofei; Ren, Yuan; Hu, Yun

2013-09-01

Identification and removal of polycyclic aromatic hydrocarbons (PAHs) were investigated at two coke plants located in Shaoguan, Guangdong Province of China. Samples of raw coking wastewaters and wastewaters from subunits of a coke production plant were analyzed using gas chromatography-mass spectrometry (GC/MS) to provide a detailed chemical characterization of PAHs. The identification and characterization of PAH isomers was based on a positive match of mass spectral data of sample peaks with those for PAH isomers in mass spectra databases with electron impact ionization mass spectra and retention times of internal reference compounds. In total, 270 PAH compounds including numerous nitrogen, oxygen, and sulfur heteroatomic derivatives were positively identified for the first time. Quantitative analysis of target PAHs revealed that total PAH concentrations in coking wastewaters were in the range of 98.5 ± 8.9 to 216 ± 20.2 μg/L, with 3-4-ring PAHs as dominant compounds. Calculation of daily PAH output from four plant subunits indicated that PAHs in the coking wastewater came mainly from ammonia stripping wastewater. Coking wastewater treatment processes played an important role in removing PAHs in coking wastewater, successfully removing 92 % of the target compounds. However, 69 weakly polar compounds, including PAH isomers, were still discharged in the final effluent, producing 8.8 ± 2.7 to 31.9 ± 6.8 g/day of PAHs with potential toxicity to environmental waters. The study of coking wastewater herein proposed can be used to better predict improvement of coke production facilities and treatment conditions according to the identification and removal of PAHs in the coke plant as well as to assess risks associated with continuous discharge of these contaminants to receiving waters.

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).

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.

Characterization of a Microbial Consortium for the Bioremoval of Polycyclic Aromatic Hydrocarbons (PAHs) in Water

PubMed Central

Blanco-Enríquez, Esmeralda G.; Zavala-Díaz de la Serna, Francisco Javier; Peralta-Pérez, María del Rosario; Ballinas-Casarrubias, Lourdes; Salmerón, Iván; Rubio-Arias, Héctor; Rocha-Gutiérrez, Beatriz A.

2018-01-01

Pollution of freshwater ecosystems from polycyclic aromatic hydrocarbons (PAHs) is a global concern. The US Environmental Protection Agency (EPA) has included the PAHs pyrene, phenanthrene, and naphthalene among the 16 priority compounds of special concern for their toxicological effects. The aim of this study was to adapt and characterize a microbial consortium from ore waste with the potential to remove these three PAHs from water. This microbial consortium was exposed to the target PAHs at levels of 5, 10, 20, 50, and 100 mg L−1 for 14 days. PAH bioremoval was measured using the analytical technique of solid phase microextraction, followed by gas chromatography mass spectrometry (SPME-GC/MS). The results revealed that up to 90% of the target PAHs can be removed from water after 14 days at a concentration level of 100 mg L−1. The predominant group of microorganisms identified at the phylum taxonomic level were the Proteobacteria, while the Actinobacteria were the predominant subgroup. The removal of phenanthrene, naphthalene, and pyrene predominantly occurred in specimens of genera Stenotrophomonas, Williamsia, and Chitinophagaceae, respectively. This study demonstrates that the use of specific microorganisms is an alternative method of reducing PAH levels in water. PMID:29757264

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.

Variations of emission characterization of PAHs emitted from different utility boilers of coal-fired power plants and risk assessment related to atmospheric PAHs.

PubMed

Wang, Ruwei; Liu, Guijian; Zhang, Jiamei

2015-12-15

Coal-fired power plants (CFPPs) represent important source of atmospheric PAHs, however, their emission characterization are still largely unknown. In this work, the concentration, distribution and gas-particle partitioning of PM10- and gas-phase PAHs in flue gas emitted from different coal-fired utility boilers were investigated. Moreover, concentration and distribution in airborne PAHs from different functional areas of power plants were studied. People's inhalatory and dermal exposures to airborne PAHs at these sites were estimated and their resultant lung cancer and skin cancer risks were assessed. Results indicated that the boiler capacity and operation conditions have significant effect on PAH concentrations in both PM10 and gas phases due to the variation of combustion efficiency, whereas they take neglected effect on PAH distributions. The wet flue gas desulphurization (WFGD) takes significant effect on the scavenging of PAH in both PM10 and gas phases, higher scavenging efficiency were found for less volatile PAHs. PAH partitioning is dominated by absorption into organic matter and accompanied by adsorption onto PM10 surface. In addition, different partitioning mechanism is observed for individual PAHs, which is assumed arising from their chemical affinity and vapor pressure. Risk assessment indicates that both inhalation and dermal contact greatly contribute to the cancer risk for CFPP workers and nearby residents. People working in workshop are exposed to greater inhalation and dermal exposure risk than people living in nearby vicinity and working office. Copyright © 2015. Published by Elsevier B.V.

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).

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.

Characterizing the PAHs in surface waters and snow in the Athabasca region: Implications for identifying hydrological pathways of atmospheric deposition.

PubMed

Birks, S J; Cho, S; Taylor, E; Yi, Y; Gibson, J J

2017-12-15

The composition of polycyclic aromatic hydrocarbons present in snow and surface waters in the Athabasca Oil Sands Region (AOSR) was characterized in order to identify major contributors to the organics detected in rivers and lakes in the region. PAH concentrations, measured by three monitoring programs in 2011, were used to compare the PAH compositions of snow and surface waters across the AOSR. The 2011 dataset includes total (dissolved+particulate) concentrations of thirty-four parent and alkylated PAH compounds in 105 snow, 272 river, and 3 lake samples. The concentration of PAHs in rivers varies seasonally, with the highest values observed in July. The timing of increases in PAH concentrations in rivers coincides with the high river discharge during the spring freshet, indicating that this major hydrological event may play an important role in delivering PAHs to rivers. However, the composition of PAHs present in rivers during this period differs from the composition of PAHs present in snow, suggesting that direct runoff and release of PAHs accumulated on snow may not be the major source of PAHs to the Athabasca River and its tributaries. Instead, snowmelt may contribute indirectly to increases in PAHs due to hydrological processes such as erosion of stream channels, remobilization of PAH-containing sediments, increased catchment runoff, and snowmelt-induced groundwater inputs during this dynamic hydrologic period. Better understanding of transformations of PAH profiles during transport along surface and subsurface flow paths in wetland-dominated boreal catchments would improve identification of potential sources and pathways in the region. The compositional differences highlight the challenges in identifying the origins of PAHs in a region with multiple potential natural and anthropogenic sources particularly when the potential transport pathways include air, soil and water. Copyright © 2017 Elsevier B.V. All rights reserved.

Analysis of the Organic Matter in Interplanetary Dust Particles: Clues to the Organic Matter in Comets, Asteroids, and Interstellar Grains

NASA Technical Reports Server (NTRS)

Flynn, G. J.; Keller, L. P.

2003-01-01

Reflection spectroscopy suggests the C- , P-, and D-types of asteroids contain abundant carbon, but these Vis-nearIR spectra are featureless, providing no information on the type(s) of carbonaceous matter. Infrared spectroscopy demonstrates that organic carbon is a significant component in comets and as grains or grain coatings in the interstellar medium. Most of the interplanetary dust particles (IDPs) recovered from the Earth s stratosphere are believed to be fragments from asteroids or comets, thus characterization of the carbon in IDPs provides the opportunity to determine the type(s) and abundance of organic matter in asteroids and comets. Some IDPs exhibit isotopic excesses of D and N-15, indicating the presence of interstellar material. The characterization of the carbon in these IDPs, and particularly any carbon spatially associated with the isotopic anomalies, provides the opportunity to characterize interstellar organic matter.

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.

Characterization of PAH matrix with monazite stream containing uranium, gadolinium and iron

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

Pal, Sangita, E-mail: sangpal@barc.gov.in; Goswami, D.; Meena, Sher Singh

2016-05-23

Uranium (U) gadolinium (Gd) and iron (Fe) containing alkaline waste simulated effluent (relevant to alkaline effluent of monazite ore) has been treated with a novel amphoteric resin viz, Polyamidehydroxamate (PAH) containing amide and hydroxamic acid groups. The resin has been synthesized in an eco-friendly manner by polymerization nad conversion to functional groups characterized by FT-IR spectra and architectural overview by SEM. Coloration of the loaded matrix and de-coloration after extraction of uranium is the special characteristic of the matrix. Effluent streams have been analyzed by ICP-AES, U loaded PAH has been characterized by FT-IR, EXAFS, Gd and Fe by X-raymore » energy values of EDXRF at 6.053 KeVand 6.405 KeV respectively. The remarkable change has been observed in Mössbauer spectrum of Fe-loaded PAH samples.« less

Occurrence and Exposure to Polycyclic Aromatic Hydrocarbons and their Derivatives in a Rural Chinese Home through Biomass Fuelled Cooking

PubMed Central

Ding, Junnan; Zhong, Junjun; Yang, Yifeng; Li, Bengang; Shen, Guofeng; Su, Yuhong; Wang, Chen; Shen, Huizhong; Wang, Bin; Wang, Rong; Huang, Ye; Zhang, Yanyan; Cao, Hongying; Zhu, Ying; Simonich, Staci L. M.; Tao, Shu

2012-01-01

The concentration and composition of PAHs emitted from biomass cooking fuel were characterized in a rural non-smoking household in northern China. Twenty-two parent PAHs (pPAHs), 12 nitro-PAHs (nPAHs), and 4 oxy-PAHs (oPAHs) were measured in the kitchen, bedroom, and outdoors during both summer and winter. The most severe contamination occurred in the kitchen in the winter, where the daily mean concentrations of pPAHs, nPAHs, and oPAHs were 7500±4100, 38±29, and 8400±9200 ng/m3, respectively. Our results suggest that the nPAHs were largely from secondary formation in ambient air while oPAHs were either from primary emission of biomass burning or secondary formation from pPAHs in the kitchen. The daily mean benzo(a)pyrene equivalent exposure concentration was as high as 200±160 ng/m3 in the winter for the housewife who did the cooking compared to 59±37 ng/m3 for the control group that did not cook. PMID:22209516

Polychlorinated biphenyls (PCB), chlorinated pesticides, and polycyclic aromatic hydrocarbons (PAHs) in environmental standard reference materials

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

Poster, D.L.; Schantz, M.M.; Parris, R.M.

1995-12-31

Standard reference materials (SRMs) are certified reference materials issued by the National Institute of Standards and Technology (NIST). Natural matrix environmental sample SRMs have been developed the Analytical Chemistry Division to assist in validating measurements for organic contaminants in the environment. Many of these are well characterized for contaminants such as polychlorinated biphenyls (PCBs), chlorinated pesticides, and polycyclic aromatic hydrocarbons (PAHs). SRM 1649, Organics in Urban Dust, is currently available with certified concentrations for 5 PAHs but because of the widespread use of this material in air pollution monitoring programs and to expand the usefulness of this material, the authorsmore » are further characterizing the material for a larger number of PAHs as well as PCBs and chlorinated pesticides. They will also soon issue a diesel particulate extract (SRM 1975) that is well characterized for PAHS, including many nitrogen substituted compounds. In addition to natural matrix materials, solutions useful for calibrating chromatographic detector response factors and retention times, and spiking sample blanks for determination of analyte recoveries, are also available. Solution SRMs currently available contain PCS congeners, chlorinated pesticides, and PAHs. New solution SRMs in preparation will contain additional chlorinated pesticides, PCB congeners (e.g., non-ortho substituted chlorobiphenyls), and perdeuterated PAHs. Recent SRM work will be presented with particular attention on the methods used for determining organic contaminant concentrations in the urban dust material and in the diesel particulate extract.« less

Analysis of "Midnight" Tracks in the Stardust Interstellar Dust Collector: Possible Discovery of a Contemporary Interstellar Dust Grain

NASA Technical Reports Server (NTRS)

Westphal, A. J.; Allen, C.; Bajit, S.; Bastien, R.; Bechtel, H.; Bleuet, P.; Borg, J.; Brenker, F.; Bridges, J.; Brownlee, D. E.;

Characterization, treatment and releases of PBDEs and PAHs in a typical municipal sewage treatment plant situated beside an urban river, East China.

PubMed

Wang, Xiaowei; Xi, Beidou; Huo, Shouliang; Sun, Wenjun; Pan, Hongwei; Zhang, Jingtian; Ren, Yuqing; Liu, Hongliang

2013-07-01

Characterization, treatment and releases of eight polybrominated diphenyl ethers (PBDEs) congeners and sixteen polycyclic aromatic hydrocarbons (PAHs) in wastewater were evaluated along the treatment processes of a typical secondary treatment municipal sewage treatment plant (STP) (in Hefei City) situated the beside Nanfei River, East China. The findings showed that the average concentrations of the total PBDEs in raw wastewater and treated effluent were 188.578 and 36.884 ng/L respectively. Brominated diphenyl ether (BDE) 209 congener, the predominant PBDE in the STP and Nanfei River, could be related to the discharge of car-industry-derived wastes. For PAHs, the average concentrations in raw wastewater and treated effluent were 5758.8 and 2240.4 ng/L respectively, with naphthalene, benzo[a]pyrene and indeno[1,2,3-c,d]pyrene being detected at the highest concentrations. PAHs mainly originate from the combustion of biomass/coal and petroleum. The STP reduced about 80% of the PBDEs and 61% of the PAHs, which were eliminated mainly by sedimentation processes. The removal rates of PBDEs/PAHs increased with the increase of their solid-water partitioning coefficients. Accordingly, the STP's effluent, containing some PBDE congeners (e.g., BDE 47, 99 and 209, etc.) and low-molecular-weight PAHs, could be an important contributor of these contaminants' input to Nanfei River. It resulted in a significant increase of PBDE/PAH concentrations and PAH toxicological risk in the river water downstream. About 4.040 kg/yr of PBDEs and 245.324 kg/yr of PAHs could be released into the Nanfei River. The current conventional wastewater treatment processes should be improved to remove the relatively low-molecular-weight PBDEs/PAHs more effectively.

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.

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.

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

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.

Current Approaches to the Treatment of Systemic-Sclerosis-Associated Pulmonary Arterial Hypertension (SSc-PAH).

PubMed

Sobanski, Vincent; Launay, David; Hachulla, Eric; Humbert, Marc

2016-02-01

Pulmonary arterial hypertension (PAH) is a severe condition causing significant morbidity and mortality in patients with systemic sclerosis (SSc). Despite the use of specific treatments, SSc-PAH survival remains poorer than in idiopathic PAH (IPAH). Recent therapeutic advances in PAH show a lower magnitude of response in SSc-PAH and a higher risk of adverse events, as compared to IPAH. The multifaceted underlying mechanisms and the multisystem nature of SSc probably explain part of the worse outcomes in SSc-PAH compared to IPAH. This review describes the current management of SSc-PAH with an emphasis on the impact of the different organ involvements in the prognosis and treatment response. An earlier detection of PAH and a better characterization of the clinical phenotypes of SSc-PAH are warranted in clinical practice and future trials. Determinants of prognosis, surrogate markers of clinical improvement or worsening, and relevance of the common endpoints used in clinical trials should be evaluated in this specific population. A multidisciplinary approach in expert referral centers is mandatory for SSc-PAH management.

Polycyclic aromatic hydrocarbons (PAHs) in wild marine organisms from South China Sea: Occurrence, sources, and human health implications.

PubMed

Ke, Chang-Liang; Gu, Yang-Guang; Liu, Qi; Li, Liu-Dong; Huang, Hong-Hui; Cai, Nan; Sun, Zhi-Wei

2017-04-15

Concentrations of 16 US EPA priority polycyclic aromatic hydrocarbons (PAHs) were measured in 15 marine wild organism species from South China Sea. The concentration (dry weight) of 16 PAHs ranged from 94.88 to 557.87ng/g, with a mean of 289.86ng/g. The concentrations of BaP in marine species were no detectable. The composition of PAHs was characterized by the 2- and 3-ring PAHs in marine species, and NA, PHE and FA were the dominant constituents. PAHs isomeric ratios indicated PAHs mainly originated from grass, wood and coal combustion, and petroleum. The human health risk assessment based on the excess cancer risk (ECR) suggested the probability of PAHs posing carcinogenic risk to human beings with consumption of marine organisms were negligible (probability<1×10 -6 ). Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Four Interstellar Dust Candidates from the Stardust Interstellar Dust Collector

NASA Technical Reports Server (NTRS)

Westphal, A. J.; Allen, C.; Bajt, S.; Bechtel, H. A.; Borg, J.; Brenker, F.; Bridges, J.; Brownlee, D. E.; Burchell, M.; Burghammer, M.;

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.

Air-water exchange of PAHs and OPAHs at a superfund mega-site.

PubMed

Tidwell, Lane G; Blair Paulik, L; Anderson, Kim A

2017-12-15

Chemical fate is a concern at environmentally contaminated sites, but characterizing that fate can be difficult. Identifying and quantifying the movement of chemicals at the air-water interface are important steps in characterizing chemical fate. Superfund sites are often suspected sources of air pollution due to legacy sediment and water contamination. A quantitative assessment of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAH (OPAHs) diffusive flux in a river system that contains a Superfund Mega-site, and passes through residential, urban and agricultural land, has not been reported before. Here, passive sampling devices (PSDs) were used to measure 60 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAH (OPAHs) in air and water. From these concentrations the magnitude and direction of contaminant flux between these two compartments was calculated. The magnitude of PAH flux was greater at sites near or within the Superfund Mega-site than outside of the Superfund Mega-site. The largest net individual PAH deposition at a single site was naphthalene at a rate of -14,200 (±5780) (ng/m 2 )/day. The estimated one-year total flux of phenanthrene was -7.9×10 5 (ng/m 2 )/year. Human health risk associated with inhalation of vapor phase PAHs and dermal exposure to PAHs in water were assessed by calculating benzo[a]pyrene equivalent concentrations. Excess lifetime cancer risk estimates show potential increased risk associated with exposure to PAHs at sites within and in close proximity to the Superfund Mega-site. Specifically, estimated excess lifetime cancer risk associated with dermal exposure and inhalation of PAHs was above 1 in 1 million within the Superfund Mega-site. The predominant depositional flux profile observed in this study suggests that the river water in this Superfund site is largely a sink for airborne PAHs, rather than a source. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Bioremediation of Mixtures of High Molecular Weight Polycyclic Aromatic Hydrocarbons

NASA Astrophysics Data System (ADS)

Xu, H.; Wu, J.; Shi, X.; Sun, Y.

2014-12-01

Although bioremediation has been considered as one of the most promising means to remove polycyclic aromatic hydrocarbons (PAHs) from polluted environments, the efficacy of PAHs bioremediation still remains challenged, especially for high molecular weight PAHs (HMW PAHs) and their mixtures. This study was focused on (a) isolation and characterization of pure strain and mixed microbial communities able to degrade HMW PAHs and (b) further evaluation of the ability of the isolated microbes to degrade HMW PAHs mixtures in the absence and presence of indigenous flora. Fluoranthene, benzo[b]fluoranthene and pyrene were selected as the representative HMW PAHs in this study. A pure bacterial strain, identified as Herbaspirillum chlorophenolicum FA1, was isolated from activated sludge. A mixed bacterial community designated as consortium-4 was isolated from petroleum contaminated soils, containing Pseudomonas sp. FbP1、Enterobacter sp. FbP2、Hydrogenophaga sp. FbP3 and Luteolibacter pohnpeiensis. FbP4. To our knowledge, this is the first study to demonstrate that bacterial strains of Herbaspirillum chlorophenolicum FA1 and Luteolibacter pohnpeiensis. FbP4 can also degrade fluoranthene, benzo[b]fluoranthene and pyrene. Experiment results showed that both strain FA1 and consortium-4 could degrade fluoranthene, benzo[b]fluoranthene and pyrene within a wide range of temperature, pH and initial PAHs concentration. Degradation of HMW PAHs mixtures (binary and ternary) demonstrated the interactive effects that can alter the rate and extent of biodegradation within a mixture. The presence of indigenous flora was found to either increase or decrease the degradation of HMW PAHs, suggesting possible synergistic or competition effects. Biodegradation kinetics of HMW PAHs for sole substrates, binary and ternary systems was evaluated, with the purpose to better characterize and compare the biodegradation process of individual HMW PAH and mixtures of HMW PAHs. Results of this study could advance our understanding of HMW PAHs biodegradation and help to develop successful bioremediation strategies. This work was supported by the National Natural Science Foundation of China (41102148), and the Specialized Research Fund for the Doctoral Program of Higher Education of China (20110091120063).

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.

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.

Ecological and health risk-based characterization of agricultural soils contaminated with polycyclic aromatic hydrocarbons in the vicinity of a chemical plant in China.

PubMed

Liu, Geng; Niu, Junjie; Guo, Wenjiong; An, Xiangsheng; Zhao, Long

2016-11-01

Polycyclic aromatic hydrocarbons (PAHs) from chemical plants can cause serious pollution of surrounding agricultural soils. A comprehensive study of agricultural soils was conducted in the vicinity of a chemical plant in China to characterize the soil PAH concentration, as well as their composition and sources. Human health and a screening-level ecological risk assessment were conducted for PAH contamination in agricultural soils. The results showed that the total concentrations of 16 priority PAHs ranged from 250.49 to 9387.26 ng g(-1), with an average of 2780.42 ng g(-1). High molecular weight PAHs (four to six rings) were the dominant component, accounting for more than 60% of all PAHs. Principal component analysis (PCA) and positive matrix factorization model (PMF) suggested that diesel emissions, coal combustion, coke ovens, and fuel combustion and gasoline emissions were the main sources of PAHs in agricultural soils. The ecological risk assessment results based on the effects range-low (ERL), the effects range-median (ERM), and the ecological screening levels (ESL) indicated that the exposure to ∑PAH16 was >ERL, >ERM, and ≥ERL and ESL at 78.1% of the soil sampling stations, and could induce biological effects in mammals. The Bapeq concentrations posed a potential carcinogenic risk to humans. Further risk management and control of soil PAHs in these agricultural soils is required to ensure the safety of the biocoenosis and human health. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) in Urban Stormwater, Madison, Wisconsin, 2005-08

USGS Publications Warehouse

Selbig, William R.

2009-01-01

Concentrations of 18 PAH compounds were characterized from six urban source areas (parking lots, feeder street, collector street, arterial street, rooftop, and strip mall) around Madison, Wisconsin. Parking lots were categorized into those that were or were not sealed. On average, chrysene, fluoranthene, and pyrene were the dominant PAH compounds in all urban stormwater samples. Geometric mean concentrations for most individual PAH compounds were significantly greater for a parking lot that was sealed than for lots that were not sealed. Results from this study are consistent with similar studies that measured PAH concentrations in urban stormwater samples in Marquette, Mich., and Madison, Wis.

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.

Stardust Interstellar Preliminary Examination II: Curating the Interstellar Dust Collector, Picokeystones, and Sources of Impact Tracks

NASA Technical Reports Server (NTRS)

Frank, David R.; Westphal, Andrew J.; Zolensky, Michael E.; Gainsforth, Zack; Butterworth, Anna L.; Bastien, Ronald K.; Allen, Carlton; Anderson, David; Bechtel, Hans A.; Sandford, Scott A.

2013-01-01

We discuss the inherent difficulties that arise during "ground truth" characterization of the Stardust interstellar dust collector. The challenge of identifying contemporary interstellar dust impact tracks in aerogel is described within the context of background spacecraft secondaries and possible interplanetary dust particles and beta-meteoroids. In addition, the extraction of microscopic dust embedded in aerogel is technically challenging. Specifically, we provide a detailed description of the sample preparation techniques developed to address the unique goals and restrictions of the Interstellar Preliminary Exam. These sample preparation requirements and the scarcity of candidate interstellar impact tracks exacerbate the difficulties. We also illustrate the role of initial optical imaging with critically important examples, and summarize the overall processing of the collection to date.

Thermodynamic and kinetic characterization of polycyclic aromatic hydrocarbons in reversed-phase liquid chromatography.

PubMed

Howerton, Samuel B; McGuffin, Victoria L

2003-07-15

The retention of six polycyclic aromatic hydrocarbons (PAHs) was characterized by reversed-phase liquid chromatography. The PAHs were detected by laser-induced fluorescence at four points along an optically transparent capillary column. The profiles were characterized in space and time using an exponentially modified Gaussian equation. The resulting parameters were used to calculate the retention factors, as well as the concomitant changes in molar enthalpy and molar volume, for each PAH on monomeric (2.7 micromol/m2) and polymeric (5.4 micromol/m2) octadecylsilica. The changes in molar enthalpy become more exothermic as ring number increases and as annelation structure becomes less condensed. The changes in molar volume become more negative as ring number increases for the planar PAHs, but are positive for the nonplanar solutes. In addition, the rate constants, as well as the concomitant activation enthalpy and activation volume, are calculated for the first time. The kinetic data demonstrate that many of the PAHs exhibit very fast transitions between the mobile and stationary phases. The transition state is very high in energy, and the activation enthalpies and volumes become greater as ring number increases and as annelation structure becomes less condensed. The changes in thermodynamic and kinetic behavior are much more pronounced for the polymeric phase than for the monomeric phase.

Enrichment and characterization of sulfate reducing, naphthalene degrading microorganisms

NASA Astrophysics Data System (ADS)

Steffen, Kümmel; Florian-Alexander, Herbst; Márcia, Duarte; Dietmar, Pieper; Jana, Seifert; Bergen Martin, von; Hans-Hermann, Richnow; Carsten, Vogt

2014-05-01

Polycyclic aromatic hydrocarbons (PAH) are pollutants of great concern due to their potential toxicity, mutagenicity and carcinogenicity. PAH are widely distributed in the environment by accidental discharges during the transport, use and disposal of petroleum products, and during forest and grass fires. Caused by their hydrophobic nature, PAH basically accumulate in sediments from where they are slowly released into the groundwater. Although generally limited by the low water solubility of PAH, microbial degradation is one of the major mechanisms leading to the complete clean-up of PAH-contaminated sites. Whereas organisms and biochemical pathways responsible for the aerobic breakdown of PAH are well known, anaerobic PAH biodegradation is less understood; only a few anaerobic PAH degrading cultures have been described. We studied the anaerobic PAH degradation in a microcosm approach to enrich anaerobic PAH degraders. Anoxic groundwater and sediment samples were used as inoculum. Groundwater samples were purchased from the erstwhile gas works facility and a former wood impregnation site. In contrast, sources of sediment samples were a former coal refining area and an old fuel depot. Samples were incubated in anoxic mineral salt medium with naphthalene as sole carbon source and sulfate as terminal electron acceptor. Grown cultures were characterized by feeding with 13C-labeled naphthalene, 16S rRNA gene sequencing using an Illumina® approach, and functional proteome analyses. Finally, six enrichment cultures able to degrade naphthalene under anoxic conditions were established. First results point to a dominance of identified sequences affiliated to the freshwater sulfate-reducing strain N47, which is a known anaerobic naphthalene degrader, in four out of the six enrichments. In those enrichments, peptides related to the pathway of anoxic naphthalene degradation in N47 were abundant. Overall the data underlines the importance of Desulfobacteria for natural attenuation of environmental contaminants. Understanding of diversity and physiology of anaerobic PAH degradation will contribute to remediation efforts of low-oxygen environments such as aquifers or river sediments.

Composition and morphology characterization of exopolymeric substances produced by the PAH-degrading fungus of Mucor mucedo.

PubMed

Jia, Chunyun; Li, Xiaojun; Allinson, Graeme; Liu, Changfeng; Gong, Zongqiang

2016-05-01

To explore the role of exopolymeric substances (EPS) in the process of polycyclic aromatic hydrocarbons (PAH) biodegradation, the characteristics of EPS isolated from a PAH-degrading fungus were investigated firstly by spectrometric determination, microscopic observation, Fourier transform-infrared spectroscopy (FT-IR), and three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM), and then the PAH-degrading ability of isolated EPS was evaluated. The EPS compositions and morphology varied significantly with the extraction methods. EPS were mainly composed of proteins, carbohydrate, and humic-like substances, and the cation exchange resin (CER)-extracted EPS were granular while other EPS samples were all powders. Heating was the most effective treatment method, followed by the CER, centrifugation, and ultrasonication methods. However, 3D-EEM data demonstrated that heating treatment makes the mycelia lyse the most. Overall, therefore, the CER was the best EPS extraction method for Mucor mucedo (M. mucedo). The PAH degradation results indicated that 87 % of pyrene and 81 % of benzo[a]pyrene (B[a]P) were removed by M. mucedo over 12 days and 9 % more pyrene and 7 % more B[a]P were reduced after CER-extracted EPS addition of 465 mg l(-1). The investigation of EPS characterization and EPS enhancing PAH biodegradation is the premise for further in-depth exploration of the role of EPS contribution to PAH biodegradation.

Bioavailability of Carbon Nanomaterial-Adsorbed Polycyclic Aromatic Hydrocarbons to Pimphales promelas: Influence of Adsorbate Molecular Size and Configuration.

PubMed

Linard, Erica N; Apul, Onur G; Karanfil, Tanju; van den Hurk, Peter; Klaine, Stephen J

2017-08-15

Despite carbon nanomaterials' (CNMs) potential to alter the bioavailability of adsorbed contaminants, information characterizing the relationship between adsorption behavior and bioavailability of CNM-adsorbed contaminants is still limited. To investigate the influence of CNM morphology and organic contaminant (OC) physicochemical properties on this relationship, adsorption isotherms were generated for a suite of polycyclic aromatic hydrocarbons (PAHs) on multiwalled carbon nanotubes (MWCNTs) and exfoliated graphene (GN) in conjunction with determining the bioavailability of the adsorbed PAHs to Pimphales promelas using bile analysis via fluorescence spectroscopy. Although it appeared that GN adsorbed PAHs indiscriminately compared to MWCNTs, the subsequent bioavailability of GN-adsorbed PAHs was more sensitive to PAH morphology than MWCNTs. GN was effective at reducing bioavailability of linear PAHs by ∼70%, but had little impact on angular PAHs. MWCNTs were sensitive to molecular size, where bioavailability of two-ringed naphthalene was reduced by ∼80%, while bioavailability of the larger PAHs was reduced by less than 50%. Furthermore, the reduction in bioavailability of CNM-adsorbed PAHs was negatively correlated with the amount of CNM surface area covered by the adsorbed-PAHs. This study shows that the variability in bioavailability of CNM-adsorbed PAHs is largely driven by PAH size, configuration and surface area coverage.

Estimation and characterization of polycyclic aromatic hydrocarbons from magnesium metallurgy facilities in China.

PubMed

Nie, Zhiqiang; Yang, Yufei; Tang, Zhenwu; Liu, Feng; Wang, Qi; Huang, Qifei

2014-11-01

Field monitoring was conducted to develop a polycyclic aromatic hydrocarbon (PAH) emission inventory for the magnesium (Mg) metallurgy industry in China. PAH emissions in stack gas and fly/bottom ash samples from different smelting units of a typical Mg smelter were measured and compared. Large variations of concentrations, congener patterns, and emission factors of PAHs during the oxidation and reduction stages in the Mg smelter were observed. The measured average emission factor (166,487 μg/t Mg) was significantly higher than those of other industrial sources. Annual emission from Mg metallurgy in 2012 in China was estimated at 116 kg (514 g BaPeq) for PAHs. The results of this study suggest that PAH emission from Mg industries should be considered by local government agencies. These data may be helpful for understanding PAH levels produced by the Mg industry and in developing a PAH inventory.

The cancer theory of pulmonary arterial hypertension

PubMed Central

Boucherat, Olivier; Vitry, Geraldine; Trinh, Isabelle; Paulin, Roxane; Provencher, Steeve; Bonnet, Sebastien

2017-01-01

Pulmonary arterial hypertension (PAH) remains a mysterious killer that, like cancer, is characterized by tremendous complexity. PAH development occurs under sustained and persistent environmental stress, such as inflammation, shear stress, pseudo-hypoxia, and more. After inducing an initial death of the endothelial cells, these environmental stresses contribute with time to the development of hyper-proliferative and apoptotic resistant clone of cells including pulmonary artery smooth muscle cells, fibroblasts, and even pulmonary artery endothelial cells allowing vascular remodeling and PAH development. Molecularly, these cells exhibit many features common to cancer cells offering the opportunity to exploit therapeutic strategies used in cancer to treat PAH. In this review, we outline the signaling pathways and mechanisms described in cancer that drive PAH cells’ survival and proliferation and discuss the therapeutic potential of antineoplastic drugs in PAH. PMID:28597757

Advances in the field of high‐molecular‐weight polycyclic aromatic hydrocarbon biodegradation by bacteria

PubMed Central

Kanaly, Robert A.; Harayama, Shigeaki

2010-01-01

Summary Interest in understanding prokaryotic biotransformation of high‐molecular‐weight polycyclic aromatic hydrocarbons (HMW PAHs) has continued to grow and the scientific literature shows that studies in this field are originating from research groups from many different locations throughout the world. In the last 10 years, research in regard to HMW PAH biodegradation by bacteria has been further advanced through the documentation of new isolates that represent diverse bacterial types that have been isolated from different environments and that possess different metabolic capabilities. This has occurred in addition to the continuation of in‐depth comprehensive characterizations of previously isolated organisms, such as Mycobacterium vanbaalenii PYR‐1. New metabolites derived from prokaryotic biodegradation of four‐ and five‐ring PAHs have been characterized, our knowledge of the enzymes involved in these transformations has been advanced and HMW PAH biodegradation pathways have been further developed, expanded upon and refined. At the same time, investigation of prokaryotic consortia has furthered our understanding of the capabilities of microorganisms functioning as communities during HMW PAH biodegradation. PMID:21255317

Reflectance spectroscopy (350-2500 nm) of solid-state polycyclic aromatic hydrocarbons (PAHs)

NASA Astrophysics Data System (ADS)

Izawa, M. R. M.; Applin, D. M.; Norman, L.; Cloutis, E. A.

2014-07-01

Polycyclic aromatic hydrocarbons (PAHs) are organic compounds based on fused aromatic rings, and are formed in a variety of astrophysical, solar nebula and planetary processes. Polycyclic aromatic hydrocarbons are known or suspected to occur in a wide variety of planetary settings including icy satellites, Titan’s hazes, carbonaceous meteorites, comet nuclei, ring particles; and terrestrial organic-rich lithologies such as coals, asphaltites, and bituminous sands. Relatively few measurements of the visible and near-infrared spectra of PAHs exist, yet this wavelength region (350-2500 nm) is widely used for remote sensing. This study presents detailed analyses of the 350-2500 nm reflectance spectra of 47 fine-grained powders of different high-purity solid-state PAHs. Spectral properties of PAHs change with variations in the number and connectivity of linked aromatic rings and the presence and type of side-groups and heterocycles. PAH spectra are characterized by three strong features near ∼880 nm, ∼1145 nm, and ∼1687 nm due to overtones of νCH fundamental stretching vibrations. Some PAHs are amenable to remote detection due to the presence of diagnostic spectral features, including: Nsbnd H stretching overtones at 1490-1515 nm in NH- and NH2-bearing PAHs, aliphatic or saturated bond Csbnd H overtone vibrations at ∼1180-1280 nm and ∼1700-1860 nm; a broad asymmetric feature between ∼1450 nm and ∼1900 nm due to Osbnd H stretching overtones in aromatic alcohols, Csbnd H and Cdbnd O combinations near ∼2000-2010 nm and ∼2060-2270 nm in acetyl and carboxyl-bearing PAHs. Other substituents such as sulphonyl, thioether ether and carboxyl heterocycles, or cyano, nitrate, and aromatic side groups, do not produce well-resolved diagnostic spectral features but do cause shifts in the positions of the aromatic Csbnd H vibrational overtone features. Fluorescence is commonly suppressed by the presence of heterocycles, side-groups and in many non-alternant PAHs. The spectral characteristics of PAHs offer the potential, under suitable circumstances, for remote characterization of the classes of PAH present and in some cases, identification of particular heterocyclic or side-group substituents.

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.

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.

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.

Infrared fluorescence from PAHs in the laboratory

NASA Technical Reports Server (NTRS)

Cherchneff, Isabelle; Barker, John R.

1989-01-01

Several celestial objects, including UV rich regions of planetary and reflection nebulae, stars, H II regions, and extragalactic sources, are characterized by the unidentified infrared emission bands (UIR bands). A few years ago, it was proposed that polycyclic aromatic hydrocarbon species (PAHs) are responsible for most of the UIR bands. This hypothesis is based on a spectrum analysis of the observed features. Comparisons of observed IR spectra with lab absorption spectra of PAHs support the PAH hypothesis. An example spectrum is represented, where the Orion Bar 3.3 micron spectrum is compared with the absorption frequencies of the PAHs Chrysene, Pyrene, and Coronene. The laser excited 3.3 micron emission spectrum is presented from a gas phase PAH (azulen). The infrared fluorescence theory (IRF) is briefly explained, followed by a description of the experimental apparatus, a report of the results, and discussion.

[Screening of pulmonary hypertension in a Spanish cohort of patients with systemic sclerosis].

PubMed

García Hernández, Francisco José; Castillo Palma, María Jesús; Montero Mateos, Enrique; González León, Rocío; López Haldón, José Eduardo; Sánchez Román, Julio

2016-01-01

Pulmonary arterial hypertension (PAH) is an important cause of morbimortality in systemic sclerosis (SSc). Evolution is worse than that of subjects with idiopathic PAH, but prognosis improves when PAH is diagnosed early. The aim of this research is to describe results of a screening program for diagnosis of pulmonary hypertension (PH) carried out in a cohort of Spanish patients with SSc. PH screening was performed by transthoracic doppler echocardiography (TTDE) in 184 patients with SSc. Patients with systolic pulmonary arterial pressure estimated by TTDE>35 mmHg were evaluated per protocol to confirm diagnosis and type of PH. PAH was diagnosed in 25 patients (13.6%). Patients with diffuse and limited SSc developed PAH in a similar degree, 9/60 (15%) vs. 16/100 (16%), with no cases among patients with SSc "sine scleroderma" or "pre-scleroderma" (P<.001). The only clinical or epidemiological data characterizing patients with PAH were older age (mean age 67 years for patients with PAH vs. 56 years for those without PAH, P=.007), limited SSc, a trend toward shorter evolution of the underlying disease (median 8 years for patients with PAH vs. 10 years for those without PAH, P=.73), and a higher frequency of positive anticentromere antibodies (16 patients [64%] with PAH vs. 70 (48,3%) without PAH, P=.19). Prevalence of PAH in SSc was high and supports the implementation of a regular screening program. Copyright © 2015 Elsevier España, S.L.U. All rights reserved.

Polycyclic aromatic hydrocarbons at fire stations: firefighters' exposure monitoring and biomonitoring, and assessment of the contribution to total internal dose.

PubMed

Oliveira, Marta; Slezakova, Klara; Alves, Maria José; Fernandes, Adília; Teixeira, João Paulo; Delerue-Matos, Cristina; Pereira, Maria do Carmo; Morais, Simone

2017-02-05

This work characterizes levels of eighteen polycyclic aromatic hydrocarbons (PAHs) in the breathing air zone of firefighters during their regular work shift at eight Portuguese fire stations, and the firefighters' total internal dose by six urinary monohydroxyl metabolites (OH-PAHs). Total PAHs (ΣPAHs) concentrations varied widely (46.4-428ng/m 3 ), mainly due to site specificity (urban/rural) and characteristics (age and layout) of buildings. Airborne PAHs with 2-3 rings were the most abundant (63.9-95.7% ΣPAHs). Similarly, urinary 1-hydroxynaphthalene and 1-hydroxyacenaphthene were the predominant metabolites (66-96% ΣOH-PAHs). Naphthalene contributed the most to carcinogenic ΣPAHs (39.4-78.1%) in majority of firehouses; benzo[a]pyrene, the marker of carcinogenic PAHs, accounted with 1.5-10%. Statistically positive significant correlations (r≥0.733, p≤0.025) were observed between ΣPAHs and urinary ΣOH-PAHs for firefighters of four fire stations suggesting that, at these sites, indoor air was their major exposure source of PAHs. Firefighter's personal exposure to PAHs at Portuguese fire stations were well below the existent occupational exposure limits. Also, the quantified concentrations of post-shift urinary 1-hydroxypyrene in all firefighters were clearly lower than the benchmark level (0.5μmol/mol) recommended by the American Conference of Governmental Industrial Hygienists. Copyright © 2016 Elsevier B.V. All rights reserved.

Pulmonary arterial hypertension associated to systemic erythematous lupus: molecular characterization of 3 cases.

PubMed

Pousada, Guillermo; Lago-Docampo, Mauro; Baloira, Adolfo; Valverde, Diana

2018-03-08

Pulmonary arterial hypertension associated with systemic lupus erythematosus (PAH-SLE) is a rare disease with a low incidence rate. In this study, PAH related genes and genetic modifiers were characterised molecularly in patients with PAH-SLE. Three patients diagnosed with PAH-SLE and 100 control individuals were analysed after signing an informed consent. Two out of the three analysed patients with PAH-SLE were carriers of pathogenic mutations in the genes BMPR2 and ENG. After an in silico analysis, pathogenic mutations were searched for in control individuals and different databases, with negative results, and they were thus functionally analysed. The third patients only showed polymorphisms in the genes BMPR2, ACVRL1 and ENG. Several genetic variants and genetic modifiers were identified in the three analysed patients. These modifiers, along with the pathogenic mutations, could lead to a more severe clinical course in patients with PAH. We present, for the first time, patients with PAH-SLE carrying pathogenic mutations in the main genes related to PAH and alterations in the genetic modifiers. Copyright © 2018 Elsevier España, S.L.U. All rights reserved.

Detection and characterization of human serum antibodies to polycyclic aromatic hydrocarbon diol-epoxide DNA adducts.

PubMed Central

Newman, M J; Light, B A; Weston, A; Tollurud, D; Clark, J L; Mann, D L; Blackmon, J P; Harris, C C

1988-01-01

The presence of serum antibodies to the diol-epoxide DNA adducts of representative polycyclic aromatic hydrocarbons (PAH), chrysene, benz[a]anthracene and benzo[a]pyrene, was determined by ELISA using serum samples obtained from normal healthy individuals. Antibodies that reacted against PAH adducted-DNA, but not against PAH-adducted protein, were found in the serum of approximately 40% of the test individuals. Specificity analysis of the antibodies demonstrated that serological cross-reactions between the benzo[a]pyrene and the chrysene diol-epoxide adducts were present. Similar cross-reactivity between the benz[a]anthracene and the chrysene adducts was observed. Sera containing antibodies that were apparently specific for each of the three PAH-DNA adducts were also identified. The presence of antibodies to PAH-DNA adducts indicates both past exposure to these carcinogenic PAH and their metabolic activation to the DNA damaging metabolites. These antibodies may prove to be useful in both retrospective and prospective epidemiological studies of various diseases associated with PAH exposure. PMID:3392204

'Rare biosphere' bacteria as key phenanthrene degraders in coastal seawaters.

PubMed

Sauret, Caroline; Séverin, Tatiana; Vétion, Gilles; Guigue, Catherine; Goutx, Madeleine; Pujo-Pay, Mireille; Conan, Pascal; Fagervold, Sonja K; Ghiglione, Jean-François

2014-11-01

By coupling DNA-SIP and pyrosequencing approaches, we identified Cycloclasticus sp. as a keystone degrader of polycyclic aromatic hydrocarbons (PAH) despite being a member of the 'rare biosphere' in NW Mediterranean seawaters. We discovered novel PAH-degrading bacteria (Oceanibaculum sp., Sneathiella sp.) and we identified other groups already known to possess this function (Alteromonas sp., Paracoccus sp.). Together with Cycloclasticus sp., these groups contributed to potential in situ phenanthrene degradation at a rate >0.5 mg l(-1) day(-1), sufficient to account for a considerable part of PAH degradation. Further, we characterized the PAH-tolerant bacterial communities, which were much more diverse in the polluted site by comparison to unpolluted marine references. PAH-tolerant bacteria were also members of the rare biosphere, such as Glaciecola sp. Collectively, these data show the complex interactions between PAH-degraders and PAH-tolerant bacteria and provide new insights for the understanding of the functional ecology of marine bacteria in polluted waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of polycyclic aromatic hydrocarbons in soil close to secondary copper and aluminum smelters.

PubMed

Hu, Jicheng; Wu, Jing; Zha, Xiaoshuo; Yang, Chen; Hua, Ying; Wang, Ying; Jin, Jun

2017-04-01

A total of 35 surface soil samples around two secondary copper smelters and one secondary aluminum smelter were collected and analyzed for 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs). The concentrations of PAHs were highest when the soil sample sites were closest to the secondary copper smelters. And, a level gradient of PAHs was observed in soil samples according to the distance from two secondary copper smelters, respectively. The results suggested that PAH concentrations in surrounding soils may be influenced by secondary copper smelters investigated, whereas no such gradient was observed in soils around the secondary aluminum smelter. Further analysis revealed that PAH patterns in soil samples also showed some difference between secondary copper and aluminum smelter, which may be attributed to the difference in their fuel and smelting process. PAH patterns and diagnostic ratios indicated that biomass burning may be also an important source of PAHs in the surrounding soil in addition to the emissions from the plants investigated.

Ultrasound assisted, thermally activated persulfate oxidation of coal tar DNAPLs.

PubMed

Peng, Libin; Wang, Li; Hu, Xingting; Wu, Peihui; Wang, Xueqing; Huang, Chumei; Wang, Xiangyang; Deng, Dayi

2016-11-15

The feasibility of ultrasound assisted, thermally activated persulfate for effective oxidation of twenty 2-6 ringed coal tar PAHs in a biphasic tar/water system and a triphasic tar/soil/water system were investigated and established. The results indicate that ultrasonic assistance, persulfate and elevated reaction temperature are all required to achieve effective oxidation of coal tar PAHs, while the heating needed can be provided by ultrasonic induced heating as well. Further kinetic analysis reveals that the oxidation of individual PAH in the biphasic tar/water system follows the first-order kinetics, and individual PAH oxidation rate is primary determined by the mass transfer coefficients, tar/water interfacial areas, the aqueous solubility of individual PAH and its concentration in coal tar. Based on the kinetic analysis and experimental results, the contributions of ultrasound, persulfate and elevated reaction temperature to PAHs oxidation were characterized, and the effects of ultrasonic intensity and oxidant dosage on PAHs oxidation efficiency were investigated. In addition, the results indicate that individual PAH degradability is closely related to its reactivity as well, and the high reactivity of 4-6 ringed PAHs substantially improves their degradability. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Evaluation of heavy metal and polycyclic aromatic hydrocarbons accumulation in plants from typical industrial sites: potential candidate in phytoremediation for co-contamination.

PubMed

Sun, Lu; Liao, Xiaoyong; Yan, Xiulan; Zhu, Ganghui; Ma, Dong

2014-11-01

The heavy metal and polycyclic aromatic hydrocarbons (PAHs) contents were evaluated in surface soil and plant samples of 18 wild species collected from 3 typical industrial sites in South Central China. The accumulative characteristics of the plant species for both heavy metal and PAHs were discussed. The simultaneous accumulation of heavy metal and PAHs in plant and soil was observed at all the investigated sites, although disparities in spatial distributions among sites occurred. Both plant and soil samples were characterized by high accumulation for heavy metal at smelting site, moderate enrichment at coke power and coal mining sites, whereas high level of PAHs (16 priority pollutants according to US Environmental Protection Agency) at coke power site, followed sequentially by coal mining and smelting sites. Based on the differences of heavy metal and PAH accumulation behaviors of the studied plant species, heavy metal and PAH accumulation strategies were suggested: Pteris vittata L. and Pteris cretica L. for As and PAHs, Boehmeria nivea (L.) Gaud for Pb, As, and PAHs, and Miscanthus floridulu (Labnll.) Warb for Cu and PAHs. These native plant species could be proposed as promising materials for heavy metal and PAHs combined pollution remediation.

Levels, composition profiles and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in sludge from ten textile dyeing plants.

PubMed

Ning, Xun-An; Lin, Mei-Qing; Shen, Ling-Zhi; Zhang, Jian-Hao; Wang, Jing-Yu; Wang, Yu-Jie; Yang, Zuo-Yi; Liu, Jing-Yong

2014-07-01

As components of synthetic dyes, polycyclic aromatic hydrocarbons (PAHs) are present as contaminants in textile dyeing sludge due to the recalcitrance in wastewater treatment process, which may pose a threat to environment in the process of sludge disposal. In order to evaluate PAHs in textile dyeing sludge, comprehensive investigation comprising 10 textile dyeing plants was undertaken. Levels, composition profiles and risk assessment of 16 EPA-priority PAHs were analyzed in this study. The total concentrations of 16 PAHs (∑16 PAHs) varied from 1463 ± 177 ng g(-1) to 16,714 ± 1,507 ng g(-1) with a mean value of 6386 ng g(-1). The composition profiles of PAHs were characterized by 3- and 4-ring PAHs, among which phenanthrene, anthracene and fluoranthene were the most dominant components. The mean benzo[a]pyrene equivalent (BaPeq) concentration of ∑16 PAHs in textile dyeing sludge was 423 ng g(-1), which was 2-3 times higher than concentrations reported for urban soil. According to ecological risk assessment, the levels of PAHs in the textile dyeing sludge may cause a significant risk to soil ecosystem after landfill or dumping on soil. Copyright © 2014 Elsevier Inc. All rights reserved.

Polycyclic aromatic hydrocarbons in sediments from the Old Yellow River Estuary, China: occurrence, sources, characterization and correlation with the relocation history of the Yellow River.

PubMed

Yuan, Zijiao; Liu, Guijian; Wang, Ruwei; Da, Chunnian

2014-11-01

The levels of 16 USEPA priority PAHs were determined in surface sediments and one dated sediment core from the abandoned Old Yellow River Estuary, China. Total PAH concentrations in the surface sediments ranged from 100.4 to 197.3 ng g(-1) dry weight and the total toxic equivalent quantity (TEQ(carc)) values of the carcinogenic PAHs were very low. An evaluation of PAH sources based on diagnostic ratios and principal component analysis suggested that PAHs in the surface sediments mainly derived from combustion sources. The total PAH concentrations altered significantly with year of deposition and showed quite different patterns of change compared with other studies: it is hypothesized that the principal cause of these changes is the relocation of the course of the Yellow River to the sea in 1976 and 1996. Copyright © 2014 Elsevier Inc. All rights reserved.

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

Halambage Upul Deepthike; Robin Tecon; Gerry van Kooten

In the wake of the 1989 Exxon Valdez oil spill, spatially and temporally spill-correlated biological effects consistent with polycyclic aromatic hydrocarbon (PAH) exposure were observed. Some works have proposed that confounding sources from local source rocks, prominently coals, are the provenance of the PAHs. Representative coal deposits along the southeast Alaskan coast (Kulthieth Formation) were sampled and fully characterized chemically and geologically. The coals have variable but high total organic carbon content, technically classifying as coals and coaly shale, and highly varying PAH contents. Even for coals with high PAH content (4000 ppm total PAHs), a PAH-sensitive bacterial biosensor demonstratesmore » nondetectable bioavailability as quantified, based on naphthalene as a test calibrant. These results are consistent with studies indicating that materials such as coals strongly diminish the bioavailability of hydrophobic organic compounds and support previous work suggesting that hydrocarbons associated with the regional background in northern Gulf of Alaska marine sediments are not appreciably bioavailable. 44 refs., 4 figs., 2 tabs.« less

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.

[The mutation analysis of PAH gene and prenatal diagnosis in classical phenylketonuria family].

PubMed

Yan, Yousheng; Hao, Shengju; Yao, Fengxia; Sun, Qingmei; Zheng, Lei; Zhang, Qinghua; Zhang, Chuan; Yang, Tao; Huang, Shangzhi

2014-12-01

To characterize the mutation spectrum of phenylalanine hydroxylase (PAH) gene and perform prenatal diagnosis for families with classical phenylketonuria. By stratified sequencing, mutations were detected in the exons and flaking introns of PAH gene of 44 families with classical phenylketonuria. 47 fetuses were diagnosed by combined sequencing with linkage analysis of three common short tandem repeats (STR) (PAH-STR, PAH-26 and PAH-32) in the PAH gene. Thirty-one types of mutations were identified. A total of 84 mutations were identified in 88 alleles (95.45%), in which the most common mutation have been R243Q (21.59%), EX6-96A>G (6.82%), IVS4-1G>A (5.86%) and IVS7+2T>A (5.86%). Most mutations were found in exons 3, 5, 6, 7, 11 and 12. The polymorphism information content (PIC) of these three STR markers was 0.71 (PAH-STR), 0.48 (PAH-26) and 0.40 (PAH-32), respectively. Prenatal diagnosis was performed successfully with the combined method in 47 fetuses of 44 classical phenylketonuria families. Among them, 11 (23.4%) were diagnosed as affected, 24 (51.1%) as carriers, and 12 (25.5%) as unaffected. Prenatal diagnosis can be achieved efficiently and accurately by stratified sequencing of PAH gene and linkage analysis of STR for classical phenylketonuria families.

Identification and characterization of epoxide hydrolase activity of polycyclic aromatic hydrocarbon-degrading bacteria for biocatalytic resolution of racemic styrene oxide and styrene oxide derivatives.

PubMed

Woo, Jung-Hee; Kwon, Tae-Hyung; Kim, Jun-Tae; Kim, Choong-Gon; Lee, Eun Yeol

2013-04-01

A novel epoxide hydrolase (EHase) from polycyclic aromatic hydrocarbon (PAH)-degrading bacteria was identified and characterized. EHase activity was identified in four strains of PAH-degrading bacteria isolated from commercial gasoline and oil-contaminated sediment based on their growth on styrene oxide and its derivatives, such as 2,3- and 4-chlorostyrene oxides, as a sole carbon source. Gordonia sp. H37 exhibited high enantioselective hydrolysis activity for 4-chlorostyrene oxide with an enantiomeric ratio of 27. Gordonia sp. H37 preferentially hydrolyzed the (R)-enantiomer of styrene oxide derivatives resulting in the preparation of a (S)-enantiomer with enantiomeric excess greater than 99.9 %. The enantioselective EHase activity was identified and characterized in various PAH-degrading bacteria, and whole cell Gordonia sp. H37 was employed as a biocatalyst for preparing enantiopure (S)-styrene oxide derivatives.

Characterization of a Naphthalene Dioxygenase Endowed with an Exceptionally Broad Substrate Specificity Toward Polycyclic Aromatic Hydrocarbons

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

Jouanneau,Y.; Meyer, C.; Jakoncic, J.

In Sphingomonas CHY-1, a single ring-hydroxylating dioxygenase is responsible for the initial attack of a range of polycyclic aromatic hydrocarbons (PAHs) composed of up to five rings. The components of this enzyme were separately purified and characterized. The oxygenase component (ht-PhnI) was shown to contain one Rieske-type [2Fe-2S] cluster and one mononuclear Fe center per {alpha} subunit, based on EPR measurements and iron assay. Steady-state kinetic measurements revealed that the enzyme had a relatively low apparent Michaelis constant for naphthalene (K{sub m} = 0.92 {+-} 0.15 {mu}M) and an apparent specificity constant of 2.0 {+-} 0.3 M{sup -1} s{sup -1}.more » Naphthalene was converted to the corresponding 1,2-dihydrodiol with stoichiometric oxidation of NADH. On the other hand, the oxidation of eight other PAHs occurred at slower rates and with coupling efficiencies that decreased with the enzyme reaction rate. Uncoupling was associated with hydrogen peroxide formation, which is potentially deleterious to cells and might inhibit PAH degradation. In single turnover reactions, ht-PhnI alone catalyzed PAH hydroxylation at a faster rate in the presence of organic solvent, suggesting that the transfer of substrate to the active site is a limiting factor. The four-ring PAHs chrysene and benz[a]anthracene were subjected to a double ring-dihydroxylation, giving rise to the formation of a significant proportion of bis-cis-dihydrodiols. In addition, the dihydroxylation of benz[a]anthracene yielded three dihydrodiols, the enzyme showing a preference for carbons in positions 1,2 and 10,11. This is the first characterization of a dioxygenase able to dihydroxylate PAHs made up of four and five rings.« less

Separation and characterization of polycyclic aromatic hydrocarbons and alkylphenols in coal derived solvents

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

Hurtubise, R.J.; Allen, T.W.; Hussain, A.

1981-03-29

Dry-column chromatography with an aluminum oxide stationary phase and a n-hexane-ether (19:1) mobile phase was used to separate polycyclic aromatic hydrocarbons (PAH) by ring size. Prior to the dry-column chromatography step, the coal derived solvents were added to an acid treated silica gel column and eluted with chloroform. This step removed pyridine-type nitrogen heterocycles. After separation of the individual ring fractions, the fractions were further separated by either thin layer chromatography (TLC) or high performance liquid chromatography (HPLC). If TLC was used, then after separation fluorescence profiles of each PAH ring fraction distributed on 30%-acetylated cellulose chromatoplates were obtained withmore » a spectrodensitometer. Measurement of fluorescence peak heights gave an approximate measure of the amount of the 3-, 4-, 5-, and 6- ring PAH. For HPLC separation, the 3- and 4- ring PAH fractions obtained from the dry-column chromatography step were separated with a ..mu..-Bondapak C/sub 18/ column and methanol:water (65:35) mobile phase. The HPLC separated PAH were characterized by chromatographic correlation factors and corrected fluorescence excitation spectra. Alkylphenols were identified in coal recycle solvent sample following separation by HPLC.« less

Distribution and transport of particle-bound polycyclic aromatic hydrocarbons in a river-influenced continental margin: the northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Adhikari, P. L.; Maiti, K.

2017-12-01

Polycyclic aromatic hydrocarbons (PAHs) are particle-reactive and get preferentially sorbed on particulate organic carbon (POC), thus, the transport and fate of POC in aquatic systems plays an important role in biogeochemical cycling of PAHs. In this study, we examine POC and PAHs in finer suspended particulate matter collected from the Louisiana coast, shelf and slope - progressively south-west transect along the direction of the Mississippi River plume, and also from a transect of Atchafalaya River. The concentrations of total particulate PAHs (ΣPAH43) varied between 0.92 to 7.04 ng/L, while POC varied between 4 to 131 µg/L. The concentrations of total particulate ΣPAH43 as well as individual PAH analytes were significantly positively correlated to the concentrations of POC which indicates that the concentrations and transport of POC plays an important role in distribution of PAHs in marine systems. The river influence, characterized by the change in salinity, had significant negative correlation with both the concentrations of particulate PAHs and POC. These results show that the Mississippi River derived particle influx can be an important vector in delivering particle-reactive hydrophobic organic pollutants such as PAHs into the river dominated continental ecosystems in the northern Gulf of Mexico. The underlying seafloor sediment PAHs' concentration and accumulation rates were not correlated to the water column particulate PAH and POC concentrations, which is attributed to re-mineralization during vertical transport, sediment resuspension/redistribution and different timescales of comparison.

World Health Organization Group I Pulmonary Hypertension: Epidemiology and Pathophysiology.

PubMed

Prins, Kurt W; Thenappan, Thenappan

2016-08-01

Pulmonary arterial hypertension (PAH) is a debilitating disease characterized by pathologic remodeling of the resistance pulmonary arteries, ultimately leading to right ventricular (RV) failure and death. In this article we discuss the definition of PAH, the initial epidemiology based on the National Institutes of Health Registry, and the updated epidemiology gleaned from contemporary registries, pathogenesis of pulmonary vascular dysfunction and proliferation, and RV failure in PAH. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterization of polycyclic aromatic hydrocarbons (PAHs) in vegetables near industrial areas of Shanghai, China: Sources, exposure, and cancer risk.

PubMed

Jia, Jinpu; Bi, Chunjuan; Zhang, Junfeng; Jin, Xiaopei; Chen, Zhenlou

2018-06-13

Dietary consumption of contaminated vegetables may contribute to polycyclic aromatic hydrocarbon (PAH) exposure in humans; however, this exposure pathway has not been examined thoroughly. This study aims to characterize the concentrations of PAHs in six types of vegetables grown near industrial facilities in Shanghai, China. We analyzed 16 individual PAHs on the US EPA priority list, and the total concentration in vegetables ranged from 65.7 to 458.0 ng g -1 in the following order: leafy vegetables (romaine lettuce, Chinese cabbage and Shanghai green cabbage) > stem vegetables (lettuce) > seed and pod vegetables (broad bean) > rhizome vegetables (daikon). Vegetable species, wind direction, and local anthropogenic emissions were determinants of PAH concentrations in the edible part of the vegetable. Using isomer ratios and principal component analysis, PAHs in the vegetables were determined to be mainly from coal and wood combustion. The sources of PAHs in the six types of vegetables varied. Daily ingestion of PAHs due to dietary consumption of these vegetables ranged from 0.71 to 14.06 ng d -1 kg -1 , with contributions from Chinese cabbage > broad bean > romaine > Shanghai green cabbage > lettuce > daikon. The daily intake doses adjusted by body weight in children were higher than those in teenagers and adults. Moreover, in adults, higher concentrations of PAHs were found in females than in males. For individuals of different age and gender, the incremental lifetime cancer risks (ILCRs) from consuming these six vegetables ranged from 4.47 × 10 -7 to 6.39 × 10 -5 . Most were higher than the acceptable risk level of 1 × 10 -6 . Our findings demonstrate that planting vegetables near industrial facilities may pose potential cancer risks to those who consume the vegetables. Copyright © 2018 Elsevier Ltd. All rights reserved.

Long-term monitoring data to describe the fate of polycyclic aromatic hydrocarbons in Deepwater Horizon oil submerged off Alabama's beaches.

PubMed

Yin, Fang; John, Gerald F; Hayworth, Joel S; Clement, T Prabhakar

2015-03-01

The 2010 Deepwater Horizon (DWH) catastrophe had considerable impact on the ∼ 50 km long sandy beach system located along the Alabama shoreline. We present a four-year dataset to characterize the temporal evolution of various polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologs trapped in the residual oil buried along the shoreline. Field samples analyzed include the first arrival oil collected from Perdido Bay, Alabama in June 2010, and multiple oil spill samples collected until August 2014. Our field data show that, as of August 2014, DWH oil is still trapped along Alabama's beaches as submerged oil, predominately in the form of surface residual oil balls (SRBs). Chemical characterization data show that various PAHs present in the spilled oil (MC252 crude) weathered by about 45% to 100% when the oil was floating over the open ocean system in the Gulf of Mexico. Light PAHs, such as naphthalenes, were fully depleted, whereas heavy PAHs, such as chrysenes, were only partially depleted by about 45%. However, the rate of PAH weathering appears to have decreased significantly once the oil was buried within the partially-closed SRB environment. Concentration levels of several heavy PAHs have almost remained constant over the past 4 years. Our data also show that evaporation was most likely the primary weathering mechanism for PAH removal when the oil was floating over the ocean, although photo-degradation and other physico-chemical processes could have contributed to some additional weathering. Chemical data presented in this study indicate that submerged oil containing various heavy PAHs (for example, parent and alkylated chrysenes) is likely to remain in the beach system for several years. It is also likely that the organisms living in these beach environments would have an increased risk of exposure to heavy PAHs trapped in the non-recoverable form of buried DWH oil spill residues. Copyright © 2014 Elsevier B.V. All rights reserved.

Management of pulmonary arterial hypertension.

PubMed

McLaughlin, Vallerie V; Shah, Sanjiv J; Souza, Rogerio; Humbert, Marc

2015-05-12

Pulmonary hypertension (PH) is common and may result from a number of disorders, including left heart disease, lung disease, and chronic thromboembolic disease. Pulmonary arterial hypertension (PAH) is an uncommon disease characterized by progressive remodeling of the distal pulmonary arteries, resulting in elevated pulmonary vascular resistance and, eventually, in right ventricular failure. Over the past decades, knowledge of the basic pathobiology of PAH and its natural history, prognostic indicators, and therapeutic options has exploded. A thorough evaluation of a patient is critical to correctly characterize the PH. Cardiac studies, including echocardiography and right heart catheterization, are key elements in the assessment. Given the multitude of treatment options currently available for PAH, assessment of risk and response to therapy is critical in long-term management. This review also underscores unique situations, including perioperative management, intensive care unit management, and pregnancy, and highlights the importance of collaborative care of the PAH patient through a multidisciplinary approach. Copyright © 2015 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

Characterization and source apportionment of PAHs from a highly urbanized river sediments based on land use analysis.

PubMed

Huang, Yanping; Liu, Min; Wang, Ruiqi; Khan, Saira Khalil; Gao, Dengzhou; Zhang, Yazhou

2017-10-01

The city-scale land use/land cover change derived by urbanization on the fates of PAHs is of great concerns recently. This study evaluated spatiotemporal variations and sources of PAHs from a highly urbanized river sediments in the Huangpu River, Shanghai. Results indicated that the concentrations of PAHs in the sediments varied greatly across locations and seasons. The concentration of Σ 16 PAHs in the dry season were 6 times higher than that in wet season. The mainstream and midstream of the Huangpu River were identified as the hotspots in both dry and wet seasons. However, 4-ring PAH compounds were dominated, contributing 42.41% ± 6.81% and 44.70 ± 7.73% in the dry and wet seasons, respectively. Multivariate statistical and land use analysis suggested that the main sources of PAHs derived from the cultivation, traffic and commercial activities. Buffer radii (<750 m) area with cultivated land, road/street and transportation and commercial and business facilities contributed significantly the PAHs in the sediment of the Huangpu River. Population density was also an important variable regulating the PAHs concentrations less than 750 m in the wet season. Risk assessment results revealed that the PAHs toxicity in the sediments was higher in dry season than in wet season. Overall, severe land use changes caused by rapid urbanization can contribute more amount of PAHs emission and complicated sources of PAHs, thus provide insights into the importance of land use types in indicating PAHs source. Copyright © 2017 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons (PAHs) in wetland soils under different land uses in a coastal estuary: toxic levels, sources and relationships with soil organic matter and water-stable aggregates.

PubMed

Xiao, Rong; Bai, Junhong; Wang, Junjing; Lu, Qiongqiong; Zhao, Qingqing; Cui, Baoshan; Liu, Xinhui

2014-09-01

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the soils from industrial, wharf, cropland, milldam and natural wetland sites to characterize their distributions, toxic levels and possible sources in the Pearl River Estuary and identify their relationships with soil organic matter (SOM) and water-stable aggregates (WSAs). Our results indicate that the average concentration of total PAHs in this region reached a moderate pollution level, which was higher than that in other larger estuaries in Asia. The average level of total PAHs in industrial soils was 1.2, 1.5, 1.6 and 2.3 times higher than those in soils from wharf, cropland, milldam and natural wetland sites, respectively. Greater accumulation of PAHs occurred in the middle and/or bottom soil layers where 3-ring PAHs were dominant. Industrial soils also exhibited the highest toxic levels with the highest toxic equivalent concentrations of PAHs, followed by wharf and milldam soils, and the cropland and wetland soils had the lowest toxicity. The diagnostic ratios suggested that PAHs primarily originated from biomass and coal combustion at industrial and milldam sites, and petroleum combustion was determined to be the primary source of PAHs at the wharf, cropland and wetland sites. Both 3-ring and 4-ring PAHs in the milldam and wharf soils were significantly positively correlated with the SOM, whereas the 4,5,6-ring PAHs and total PAHs in industrial soils and the 2-ring PAHs in cropland soils were significantly negatively correlated with the SOM. In addition, large WSAs also exhibited a significant positive correlation with PAHs. Copyright © 2014 Elsevier Ltd. 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

PHOTOACTIVATED TOXICITY IN AMPHIPODS COLLECTED FROM POLYCYCLIC AROMATIC HYDROCARBON-CONTAMINATED SITES

EPA Science Inventory

The risk of photo-activated PAH toxicity in contaminated aquatic systems has not been well characterized. To better indicate this potential, amphipods (Gammarus spp.) were collected from two PAH contaminated sites (Hog Island and USX), as well as a reference site (Chipmunk Cove)...

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.

Levels and patterns of polycyclic aromatic hydrocarbons (PAHs) in soils after forest fires in South Korea.

PubMed

Kim, Eun Jung; Choi, Sung-Deuk; Chang, Yoon-Seok

2011-11-01

To investigate the influence of biomass burning on the levels of polycyclic aromatic hydrocarbons (PAHs) in soils, temporal trends and profiles of 16 US Environmental Protection Agency priority PAHs were studied in soil and ash samples collected 1, 5, and 9 months after forest fires in South Korea. The levels of PAHs in the burnt soils 1 month after the forest fires (mean, 1,200 ng/g dry weight) were comparable with those of contaminated urban soils. However, 5 and 9 months after the forest fires, these levels decreased considerably to those of general forest soils (206 and 302 ng/g, respectively). The burnt soils and ash were characterized by higher levels of light PAHs with two to four rings, reflecting direct emissions from biomass burning. Five and 9 months after the forest fires, the presence of naphthalene decreased considerably, which indicates that light PAHs were rapidly volatilized or degraded from the burnt soils. The temporal trend and pattern of PAHs clearly suggests that soils in the forest-fire region can be contaminated by PAHs directly emitted from biomass burning. However, the fire-affected soils can return to the pre-fire conditions over time through the washout and wind dissipation of the ash with high content of PAHs as well as vaporization or degradation of light PAHs.

Exposure Assessment of Polycyclic Aromatic Hydrocarbon (PAHs) in Childcare Centers of Muang, Nakhon Ratchasima

NASA Astrophysics Data System (ADS)

Jitlada, C.; Pentamwa, P.

2018-03-01

This study aims to characterize airborne polycyclic aromatic hydrocarbons (PAHs) as of particulate and vapor phases variation. The samples were collected from the childcare centers where divided into urban and rural areas in Nakhon Ratchasima Province of Thailand. The airborne samples were collected from five childcare centers during the dry season in the year 2017. The PAHs species were determined by the gas chromatography and mass spectroscopy (GS/MS) method. Results show that the total concentrations of PAHs were higher than vapor phase that both similar in urban area and rural area. The dominant PAHs compounds of both urban and rural areas were benzo(a)pyrene, benzo(a,h)anthracene and indeno(1,2,3-cd)pyrene, respectively. Furthermore, the concentrations of PAHs in municipality (urban) childcare centers were higher than rural childcare centers area of Nakhon Ratchasima province. The risks associated with exposure to PAHs were evaluated using the TEF approach. The estimated value of lifetime lung cancer risks children in urban were significantly (p < 0.05) 2 times of children in rural, thus demonstrating that exposure to PAHs at levels found at urban site may be cause potential health risks.

Degradation of polycyclic aromatic hydrocarbons in crumb tyre rubber catalysed by rutile TiO2 under UV irradiation.

PubMed

Yu, Kai; Huang, Linyue; Lou, Lan-Lan; Chang, Yue; Dong, Yanling; Wang, Huan; Liu, Shuangxi

2015-01-01

The polycyclic aromatic hydrocarbons (PAHs) in crumb tyre rubber were firstly degraded under UV irradiation in the presence of rutile TiO2 and hydrogen peroxide. The effects of light intensity, catalyst amount, oxidant amount, initial pH value, co-solvent content, and reaction time on degradation efficiency of typical PAHs in crumb tyre rubber were studied. The results indicated that UV irradiation, rutile TiO2, and hydrogen peroxide were beneficial to the degradation of PAHs and co-solvent could accelerate the desorption of PAHs from crumb tyre rubber. Up to 90% degradation efficiency of total 16 PAHs could be obtained in the presence of rutile TiO2 (1 wt%) and hydrogen peroxide (1.0 mL) under 1800 µW cm(-2) UV irradiation for 48 h. The high molecular weight PAHs (such as benz(a)pyrene) were more difficult to be degraded than low molecular weight PAHs (such as phenanthrene, chrysene). Moreover, through the characterization of reaction solution and degradation products via GC-MS, it was proved that the PAHs in crumb tyre rubber were successfully degraded.

Input and behavior of polycyclic aromatic hydrocarbons in arable, fallow, and forest soils of the taiga zone (Tver oblast)

NASA Astrophysics Data System (ADS)

Zhidkin, A. P.; Gennadiev, A. N.; Koshovskii, T. S.

2017-03-01

Contents of 11 most prevalent polycyclic aromatic hydrocarbons (PAHs) in snow and soils of arable, fallow, and forest areas significantly remote from impact technogenic sources of polyarenes have been examined in the Torzhok district of Tver oblast. From the analysis of snow samples, the volumes and composition of PAHs coming from the atmosphere onto the areas of different land use have been determined. Light hydrocarbons prevail in PAHs. They make up 65-70% of total PAHs; their share in soils reaches almost 95%. An increase in the content of PAHs is revealed in fallow soils compared to arable and afforested areas. A direct relationship is revealed between the lateral distribution of total PAHs and the content of organic carbon. The distribution of total PAHs is surface-accumulative in forest soils, mainly uniform in arable soils, and deepaccumulative in fallow soils. PAH groups characterized by similar radial distributions and ratios between their reserves in snow and soils are distinguished: (1) fluorene and phenanthrene, (2) biphenyl and naphthalene, (3) benzo(a)anthracene, chrysene, perylene, and benzo[ a]pyrene, and (4) anthracene and benzo[ ghi]pyrene.

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.

Characterization of particulate polycyclic aromatic hydrocarbons in an urban atmosphere of central-southern Spain.

PubMed

Villanueva, Florentina; Tapia, Araceli; Cabañas, Beatriz; Martínez, Ernesto; Albaladejo, José

2015-12-01

Over 1-year period, 13 polycyclic aromatic hydrocarbons (PAHs) associated with particulate matter PM10 have been monitored for the first time in the atmosphere of Ciudad Real, situated at the central-southern Spain. PM10-bound PAHs were collected using a high-volume sampler from autumn 2012 to summer 2013 and were analyzed by HPLC with fluorescence detector. The most abundant PAHs were pyrene, chrysene, benzo[b]fluoranthene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene. The ∑PAH concentrations in Ciudad Real were 888, 368, 259 and 382 pg m(-3) for winter, spring, summer and autumn seasons, respectively. The diurnal variation of PAH was also investigated presenting the highest concentrations during the evening (19:00-23:00). Benzo[a]pyrene concentrations ranged from 2.4 to 110 pg m(-3), these values are lower than the target value proposed by the European legislation, 1 ng m(-3). Diagnostic ratios were used to identify potential sources of PAHs. Results suggest that vehicle emissions are the major source of identified PAHs, with a higher contribution of diesel engines although other anthropogenic sources could also have an impact on the PAH levels.

Bioremediation of high molecular weight polyaromatic hydrocarbons co-contaminated with metals in liquid and soil slurries by metal tolerant PAHs degrading bacterial consortium.

PubMed

Thavamani, Palanisami; Megharaj, Mallavarapu; Naidu, Ravi

2012-11-01

Bioremediation of polyaromatic hydrocarbons (PAH) contaminated soils in the presence of heavy metals have proved to be difficult and often challenging due to the ability of toxic metals to inhibit PAH degradation by bacteria. In this study, a mixed bacterial culture designated as consortium-5 was isolated from a former manufactured gas plant (MGP) site. The ability of this consortium to utilise HMW PAHs such as pyrene and BaP as a sole carbon source in the presence of toxic metal Cd was demonstrated. Furthermore, this consortium has proven to be effective in degradation of HMW PAHs even from the real long term contaminated MGP soil. Thus, the results of this study demonstrate the great potential of this consortium for field scale bioremediation of PAHs in long term mix contaminated soils such as MGP sites. To our knowledge this is the first study to isolate and characterize metal tolerant HMW PAH degrading bacterial consortium which shows great potential in bioremediation of mixed contaminated soils such as MGP.

Spatial and temporal variations and mobile source emissions of polycyclic aromatic hydrocarbons in Quito, Ecuador

PubMed Central

Brachtl, Megan V.; Durant, John L.; Perez, Carlos Paez; Oviedo, Jorge; Sempertegui, Fernando; Naumova, Elena N.; Griffiths, Jeffrey K.

2009-01-01

Motor vehicles are a major source of air pollution in Quito, Ecuador; however, little work has been done to characterize spatial and temporal variations in traffic-related pollutants, or to measure pollutants in vehicle emissions. We measured PAH continuously for one year at two residential sites in Quito, and PAH and traffic patterns for one week near a busy roadway. Morning rush-hour traffic and temperature inversions caused daily PAH maxima between 06:00 and 08:00. SO2, NOx, CO, and PM2.5 behaved similarly. At the residential sites PAH levels during inversions were 2–3-fold higher than during the afternoon, and 10–16-fold higher than 02:00–03:00 when levels were lowest. In contrast, at the near-roadway site, PAH concentrations were 3–6-fold higher than at the residential sites, and the effects of inversions were less pronounced. Cars and buses accounted for >95% of PAH at the near-roadway site. Near-roadway PAH concentrations were comparable to other polluted cities. PMID:19004535

Pulmonary arterial hypertension: Specialists’ knowledge, practices, and attitudes of genetic counseling and genetic testing in the USA

PubMed Central

Jacher, Joseph E.; Martin, Lisa J.; Chung, Wendy K.; Loyd, James E.; Nichols, William C.

2017-01-01

Pulmonary arterial hypertension (PAH) is characterized by obstruction of pre-capillary pulmonary arteries, which leads to sustained elevation of pulmonary arterial pressure. Identifying those at risk through early interventions, such as genetic testing, may mitigate disease course. Current practice guidelines recommend genetic counseling and offering genetic testing to individuals with heritable PAH, idiopathic PAH, and their family members. However, it is unclear if PAH specialists follow these recommendations. Thus, our research objective was to determine PAH specialists’ knowledge, utilization, and perceptions about genetic counseling and genetic testing. A survey was designed and distributed to PAH specialists who primarily work in the USA to assess their knowledge, practices, and attitudes about the genetics of PAH. Participants’ responses were analyzed using parametric and non-parametric statistics and groups were compared using the Wilcoxon rank sum test. PAH specialists had low perceived and actual knowledge of the genetics of PAH, with 13.2% perceiving themselves as knowledgeable and 27% actually being knowledgeable. Although these specialists had positive or ambivalent attitudes about genetic testing and genetic counseling, they had poor utilization of these genetic services, with almost 80% of participants never or rarely ordering genetic testing or referring their patients with PAH for genetic counseling. Physicians were more knowledgeable, but had lower perceptions of the value of genetic testing and genetic counseling compared to non-physicians (P < 0.05). The results suggest that increased education and awareness is needed about the genetics of PAH as well as the benefits of genetic testing and genetic counseling for individuals who treat patients with PAH. PMID:28597770

Stardust Interstellar Preliminary Examination (ISPE)

NASA Technical Reports Server (NTRS)

Westphal, A. J.; Allen, C.; Bajt, S.; Basset, R.; Bastien, R.; Bechtel, H.; Bleuet, P.; Borg, J.; Brenker F.; Bridges, J.

2009-01-01

In January 2006 the Stardust sample return capsule returned to Earth bearing the first solid samples from a primitive solar system body, C omet 81P/Wild2, and a collector dedicated to the capture and return o f contemporary interstellar dust. Both collectors were approximately 0.1m(exp 2) in area and were composed of aerogel tiles (85% of the co llecting area) and aluminum foils. The Stardust Interstellar Dust Col lector (SIDC) was exposed to the interstellar dust stream for a total exposure factor of 20 m(exp 2-) day during two periods before the co metary encounter. The Stardust Interstellar Preliminary Examination ( ISPE) is a three-year effort to characterize the collection using no ndestructive techniques. The ISPE consists of six interdependent proj ects: (1) Candidate identification through automated digital microsco py and a massively distributed, calibrated search (2) Candidate extr action and photodocumentation (3) Characterization of candidates thro ugh synchrotronbased FourierTranform Infrared Spectroscopy (FTIR), S canning XRay Fluoresence Microscopy (SXRF), and Scanning Transmission Xray Microscopy (STXM) (4) Search for and analysis of craters in f oils through FESEM scanning, Auger Spectroscopy and synchrotronbased Photoemission Electron Microscopy (PEEM) (5) Modeling of interstell ar dust transport in the solar system (6) Laboratory simulations of h ypervelocity dust impacts into the collecting media

Profiles and removal efficiency of polycyclic aromatic hydrocarbons by two different types of sewage treatment plants in Hong Kong.

PubMed

Man, Yu Bon; Chow, Ka Lai; Cheng, Zhang; Mo, Wing Yin; Chan, Yung Hau; Lam, James Chung Wah; Lau, Frankie Tat Kwong; Fung, Wing Cheong; Wong, Ming Hung

2017-03-01

Sewage discharge could be a major source of polycyclic aromatic hydrocarbons (PAHs) in the coastal waters. Stonecutters Island and Shatin Sewage Treatment Works (SCISTW and STSTW) in Hong Kong, adopted chemically enhanced primary treatment and biological treatment, respectively. This study aimed at (1) determining the removal efficiencies of PAHs, (2) comparing the capabilities in removing PAHs, and (3) characterizing the profile of each individual PAHs, in the two sewage treatment plants (STPs). Quantification of 16 PAHs was conducted by a Gas Chromatography. The concentrations of total PAHs decreased gradually along the treatment processes (from 301±255 and 307±217ng/L to 14.9±12.1 and 63.3±54.1ng/L in STSTW and SCISTW, respectively). It was noted that STSTW was more capable in removing total PAHs than SCISTW with average total removal efficiency 94.4%±4.12% vs. 79.2%±7.48% (p<0.05). The removal of PAHs was probably due to sorption in particular matter, confirmed by the higher distribution coefficient of individual and total PAHs in solid samples (dewatered sludge contained 92.5% and 74.7% of total PAHs in SCISTW and STSTW, respectively) than liquid samples (final effluent-total contained 7.53% and 25.3% of total PAHs in STSTW and SCISTW, respectively). Despite the impressive capability of STSTW and SCISTW in removing PAHs, there was still a considerable amount of total PAHs (1.85 and 39.3kg/year, respectively for the two STPs) being discharged into Hong Kong coastal waters, which would be an environmental concern. Copyright © 2016. Published by Elsevier B.V.

Characteristics of polycyclic aromatic hydrocarbons in PM2.5 emitted from different cooking activities in China.

PubMed

Li, Yun-Chun; Qiu, Jia-Qian; Shu, Man; Ho, Steven Sai Hang; Cao, Jun-Ji; Wang, Ge-Hui; Wang, Xian-Xiang; Zhao, Xiao-Qing

2018-02-01

Nineteen polycyclic aromatic hydrocarbons (PAHs) in PM 2.5 emitted from five different cooking activities were characterized, and their influencing factors were determined. The total quantified particle-bounded PAH concentrations (ΣPAHs) in the airs from the cooking activities were 4.2-36.5-fold higher than those in corresponding backgrounds. The highest ΣPAHs were seen in cafeteria frying (783 ± 499 ng/m 3 ), followed by meat roasting (420 ± 191 ng/m 3 ), fish roasting (210 ± 105 ng/m 3 ), snack-street boiling (202 ± 230 ng/m 3 ), and cafeteria boiling (150 ± 65 ng/m 3 ). The main influencing factors on the PAH emissions were cooking methods, fat contents in raw materials, and oil consumptions. Four- to six-ringed PAHs had the highest contributions to the ΣPAHs (avg. 87.5%). Diagnostic ratios of individual PAH were similar between the two charbroiling and other three conventional Chinese cooking methods, respectively, demonstrating the dominance of cooking methods in the PAH emissions. Remarkably high benzo(b)fluoranthene/benzo(k)fluoranthene (BbF/BkF) ratio (8.31) was seen in the snack-street boiling, attributed to the coal combustion as cooking fuel. Both fluoranthene/(fluoranthene + pyrene) [FLT/(FLT + PYR)] and benzo(a)anthracene/(benzo(a)anthracene + chrysene) [BaA/(BaA + CHR)] ratios were higher for the oil-based cooking than those from the water-based ones. In addition, two ratios of indeno(1,2,3-cd)pyrene/(indeno(1,2,3-cd)pyrene + benzo(g,h,i)perylene) [IPY/(IPY + BPE)] and benzo(a)pyrene/(benzo(a)pyrene + benzo(g,h,i)perylene) [BaP/(BaP + BPE)] were higher for two charbroiling than the three conventional Chinese cooking methods. The characterization work in this study is particularly important since cooking is a potential contributor of atmospheric PAHs in urban China. Carcinogenic potencies of PAHs were assessed by comparison with the air quality guideline and health risk estimation. The BaP and BaP equivalent were higher for the oil-based than the water-based cooking activities.

Preparation and characterization of the nanoporous ultrathin multilayer films based on molybdenum polyoxometalate (Mo 38) n

NASA Astrophysics Data System (ADS)

Wang, L.; Jiang, M.; Wang, E. B.; Duan, L. Y.; Hao, N.; Lan, Y.; Xu, L.; Li, Z.

2003-11-01

Ultrathin multilayer films of the wheel-shaped molybdenum polyoxometalate cluster (Mo 38) n and poly(allylamine hydrochloride)(PAH) have been prepared by the layer-by-layer (LbL) self-assembly method. The ((Mo 38) n/PAH) m multilayer films have been characterized by X-ray photoelectron spectra (XPS) and atomic force microscopy (AFM). UV-VIS measurements reveal regular film growth with each (Mo 38) n adsorption. The electrochemistry behavior of the film at room temperature was investigated.

Assessment of dioxin-like activity in ambient air particulate matter using recombinant yeast assays

NASA Astrophysics Data System (ADS)

Olivares, Alba; van Drooge, Barend L.; Pérez Ballesta, Pascual; Grimalt, Joan O.; Piña, Benjamin

2011-01-01

Ectopic activation of the aryl hydrocarbon receptor (AhR), also known as dioxin-like activity, is a major component of the toxicity associated with polycyclic aromatic hydrocarbons (PAH). Filtration of ambient air particulate matter through PM 10 filters followed by chemical determination of PAH concentrations and a yeast-based bioassay (RYA) were combined to evaluate and characterize dioxin-like activity in ambient air. Samples were collected in a semirural area of Northern Italy between September 2008 and February 2009. Total PAH contents ranged between 0.3 ng m -3 and 34 ng m -3 and were in correlation with seasonal variations of meteorological conditions and combustion processes. Dioxin-like activity values in air samples showed an excellent correlation (0.71 < R2 < 0.86) with the observed PAH concentrations and the predicted toxicity equivalents for PAH. This RYA-bioassay reported in the present study provides a simple and low-cost routine control for toxic PAH emissions, even at background air concentration levels.

Characterization of TSP-bound n-alkanes and polycyclic aromatic hydrocarbons at rural and urban sites of Tianjin, China.

PubMed

Wu, Shui-Ping; Tao, Shu; Zhang, Zhi-Huan; Lan, Tian; Zuo, Qian

2007-05-01

Total suspended particle (TSP) was collected and analyzed at rural and urban sites in Tianjin, China during the domestic heating season (from 15 November to 15 March) of 2003/4 for n-alkanes and 16 polycyclic aromatic hydrocarbons (PAHs). The normalized distribution of n-alkanes with the peak at C22, C23, C24 or C25 suggested that fossil fuel utilization was the major source of particulate n-alkanes at both sites. PAHs normalized distribution for each sample was similar and the higher molecular weight PAH dominated the profile (around 90%) indicating a stronger combustion source at both sites. Precipitation and wind were the most important meteorological factors influencing TSP and PAHs atmospheric concentrations. In the urban area the emission height had significant influence on PAHs levels at different heights under the relative stable atmospheric conditions. Coal combustion was the major source for TSP-bound PAHs at both sites based on some diagnostic ratios.

Theoretical Calculation of the Uv-Vis Spectral Band Locations of Pahs with Unknown Syntheses Procedures and Prospective Carcinogenic Activity

NASA Astrophysics Data System (ADS)

Ona-Ruales, Jorge Oswaldo; Ruiz-Morales, Yosadara

2017-06-01

Annellation Theory and ZINDO/S semiempirical calculations have been used for the calculation of the locations of maximum absorbance (LMA) of the Ultraviolet-Visible (UV-Vis) of 31 C_{34}H_{16} PAHs (molecular mass 424 Da) with unknown protocols of synthesis. The presence of benzo[a]pyrene bay-like regions and dibenzo[a,l]pyrene fjord-like regions in several of the structures that could be linked to an enhancement of the biological behavior and carcinogenic activity stresses the importance of C_{34}H_{16} PAHs in fields like molecular biology and cancer research. In addition, the occurrence of large PAHs in oil asphaltenes exemplifies the importance of these calculations for the characterization of complex systems. The C_{34}H_{16} PAH group is the largest molecular mass group of organic compounds analyzed so far following the Annellation Theory and ZINDO/S methodology. Future analysis using the same approach will provide evidence regarding the LMA of other high molecular mass PAHs.

Measurement of the spectral signature of small carbon clusters at near and far infrared wavelengths

NASA Technical Reports Server (NTRS)

Tarter, J.; Saykally, R.

1991-01-01

A significant percentage of the carbon inventory of the circumstellar and interstellar media may be in the form of large refractory molecules (or small grains) referred to as carbon clusters. At the small end, uneven numbers of carbon atoms seem to be preferred, whereas above 12 atoms, clusters containing an even number of carbon atoms appear to be preferred in laboratory chemistry. In the lab, the cluster C-60 appears to be a particularly stable form and has been nicknamed Bucky Balls because of its resemblance to a soccer ball and to geodesic domes designed by Buckminster Fuller. In order to investigate the prevalence of these clusters, and their relationship to the polycyclic aromatic hydrocarbons (PAHs) that have become the newest focus of IR astronomy, it is necessary to determine the spectroscopic characteristics of these clusters at near and far infrared wavelengths. Described here is the construction of a near to far IR laser magnetic resonance spectrometer that has been built at the University of California Berkeley in order to detect and characterize these spectra. The equipment produces carbon clusters by laser evaporation of a graphitic target. The clusters are then cooled in a supersonic expansion beam in order to simulate conditions in the interstellar medium (ISM). The expansion beam feeds into the spectrometer chamber and permits concentrations of clusters sufficiently high as to permit ultra-high resolution spectroscopy at near and far IR wavelengths. The first successful demonstration of this apparatus occurred last year when the laboratory studies permitted the observational detection of C-5 in the stellar outflow surrounding IRC+10216 in the near-IR. Current efforts focus on reducing the temperature of the supersonic expansion beam that transport the C clusters evaporated from a graphite target into the spectrometer down to temperatures as low as 1 K.

Isolation and characterization of bacteria capable of degrading polycyclic aromatic hydrocarbons (PAHs) and organophosphorus pesticides from PAH-contaminated soil in Hilo, Hawaii.

PubMed

Seo, Jong-Su; Keum, Young-Soo; Harada, Renee M; Li, Qing X

2007-07-11

Nineteen bacterial strains were isolated from petroleum-contaminated soil in Hilo, HI, and characterized by two different spray-plated methods, turbidity test in liquid medium, and 16S rRNA gene sequence analysis. Analysis of the soil showed 13 polycyclic aromatic hydrocarbons (PAHs) in a range from 0.6 to 30 mg/kg of dry weight each and 12 PAH metabolites. Five distinct bacterial strains (C3, C4, P1-1, JS14, and JS19b1) selected from preliminary plating and turbidity tests were further tested for PAH degradation through single PAH degradation assay. Strains C3, C4, and P1-1 degraded phenanthrene (40 mg/L) completely during 7 days of incubation. Strain JS14 degraded fluoranthene (40 mg/L) completely during 10 days of incubation. Strain JS19b1 degraded 100% of phenanthrene (40 mg/L) in 7 days, 77% of fluorene (40 mg/L) in 14 days, 97% of fluoranthene (40 mg/L) in 10 days, and 100% of pyrene (40 mg/L) in 14 days. Turbidity tests showed that strains P1-1, JS14, and JS19b1 utilized several organophosphorus pesticides as growth substrate. P1-1 can degrade carbofenothion, chlorfenvinphos, diazinon, fonofos, and pirimiphos-methyl. JS14 can transform chlorfenvinphos and diazinon. JS19b1 can break down diazinon, pirimiphos-methyl, and temephos.

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.

Maternal occupational exposure to polycyclic aromatic hydrocarbons and craniosynostosis among offspring in the National Birth Defects Prevention Study.

PubMed

O'Brien, Jacqueline L; Langlois, Peter H; Lawson, Christina C; Scheuerle, Angela; Rocheleau, Carissa M; Waters, Martha A; Symanski, Elaine; Romitti, Paul A; Agopian, A J; Lupo, Philip J

2016-01-01

Evidence in animal models and humans suggests that exposure to polycyclic aromatic hydrocarbons (PAHs) may lead to birth defects. To our knowledge, this relationship has not been evaluated for craniosynostosis, a birth defect characterized by the premature closure of sutures in the skull. We conducted a case-control study to examine associations between maternal occupational exposure to PAHs and craniosynostosis. We used data from craniosynostosis cases and control infants in the National Birth Defects Prevention Study (NBDPS) with estimated delivery dates from 1997 to 2002. Industrial hygienists reviewed occupational data from the computer-assisted telephone interview and assigned a yes/no rating of probable occupational PAH exposure for each job from 1 month before conception through delivery. We used logistic regression to assess the association between occupational exposure to PAHs and craniosynostosis. The prevalence of exposure was 5.3% in case mothers (16/300) and 3.7% in control mothers (107/2,886). We observed a positive association between exposure to PAHs during the 1 month before conception through the third month of pregnancy and craniosynostosis (odds ratio [OR] = 1.75; 95% confidence interval [CI], 1.01-3.05) after adjusting for maternal age and maternal education. The number of cases for each craniosynostosis subtype limited subtype analyses to sagittal craniosynostosis; the odds ratio remained similar (OR = 1.76, 95% CI, 0.82-3.75), but was not significant. Our findings support a moderate association between maternal occupational exposure to PAHs and craniosynostosis. Additional work is needed to better characterize susceptibility and the role PAHs may play on specific craniosynostosis subtypes. © 2015 Wiley Periodicals, Inc.

Diurnal variations of ambient particulate wood burning emissions and their contribution to the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) in Seiffen, Germany

NASA Astrophysics Data System (ADS)

Poulain, L.; Iinuma, Y.; Müller, K.; Birmili, W.; Weinhold, K.; Brüggemann, E.; Gnauk, T.; Hausmann, A.; Löschau, G.; Wiedensohler, A.; Herrmann, H.

2011-12-01

Residential wood burning is becoming an increasingly important cause of air quality problems since it has become a popular source of alternative energy to fossil fuel. In order to characterize the contribution of residential wood burning to local particle pollution, a field campaign was organized at the village of Seiffen (Saxony, Germany). During this campaign, an Aerosol Mass Spectrometer (AMS) was deployed in parallel to a PM1 high volume filter sampler. The AMS mass spectra were analyzed using Positive Matrix Factorization (PMF) to obtain detailed information about the organic aerosol (OA). Biomass-burning organic aerosol (BBOA), Hydrocarbon-like organic aerosol (HOA), and Oxygenated Organic Aerosol (OOA) were identified and represented 20%, 17% and 62% of total OA, respectively. Additionally, Polycyclic Aromatic Hydrocarbons (PAH) were measured by the AMS with an average concentration of 10 ng m-3 and short term events of extremely high PAH concentration (up to 500 ng m-3) compared to the mean PAH value were observed during the whole measurement period. A comparison with the results from PM1 filter samples showed that the BBOA factor and the AMS PAH are good indicators of the total concentration of the different monosaccharide anhydrides and PAH measured on the filter samples. Based on its low correlation with CO and the low car traffic, the HOA factor was considered to be related to residential heating using liquid fuel. An influence of the time of the week (week vs. weekend) on the diurnal profiles of the different OA components was observed. The weekdays were characterized by two maxima; a first one early in the morning and a stronger one in the evening. During the weekend days, the different OA components principally reached only one maximum in the afternoon. Finally, the PAH emitted directly from residential wood combustion was estimated to represent 1.5% of the total mass of the BBOA factor and around 62% of the total PAH concentration measured at Seiffen. This result highlights the important contribution of residential wood combustion to air quality and PAH emissions at the sampling place, which might have a significant impact on human health. Moreover, it also emphasizes the need for a better time resolution of the chemical characterization of toxic particulate compounds in order to provide more information on variations of the different sources through the days as well as to better estimate the real human exposure.

Characterization of parent and oxygenated-polycyclic aromatic hydrocarbons (PAHs) in Xi'an, China during heating period: An investigation of spatial distribution and transformation.

PubMed

Wang, Jingzhi; Hang Ho, Steven Sai; Huang, Rujin; Gao, Meiling; Liu, Suixin; Zhao, Shuyu; Cao, Junji; Wang, Gehui; Shen, Zhenxing; Han, Yongming

2016-09-01

Polycyclic aromatic hydrocarbons (PAHs) and its oxygenated derivatives (OPAHs) are toxins in PM2.5. Little information has been known for their transformation in the ambient airs. In this study, PM2.5 samples were collected at 19 sampling sites in Xi'an, China during the heating period, which is classified into: urban residential, university, commercial area, suburban region, and industry. Organic compounds including PAHs, OPAHs, hopanes and cholestanes were quantified. The average of total quantified PAHs and OPAHs concentrations were 196.5 ng/m(3) and 29.4 ng/m(3), respectively, which were consistent with other northern cities in China. Statistical analyses showed that there were significant differences on the distributions of PAHs between urban and suburban regions. The industry also had distinguishable profiles compared with urban residential and commercial area for OPAHs. The greater diversity of OPAHs than PAHs might be due to different primary emission sources and transformation and degradation pathways. The ratios of OPAHs to the corresponding parent PAHs, including 9-fluorenone/fluorene, anthraquinone/anthracene, benz[a]anthracene-7,12-dione/benzo[a]anthracene were 6.2, 12.7, and 1.4, respectively, which were much higher than those for the fresh emissions from coal combustion and biomass burning. These prove the importance of secondary formation and transformation of OPAHs in the ambient airs. Biomarkers such as retene, cyclopenta[CD]pyrene and αα-homohopane were characterized for the source apportionment. With Positive Matrix Factorization (PMF) model analysis, biomass burning was recognized as the most dominant pollution sources for PAHs during the heading period, which accounted for a contribution of 37.1%. Vehicle emission (22.8%) and coal combustion (22.6%) were also contributors in Xi'an. Copyright © 2016 Elsevier Ltd. All rights reserved.

The impact of selected soil organic matter fractions on the PAH accumulation in the agricultural soils from areas of different anthropopressure.

PubMed

Klimkowicz-Pawlas, Agnieszka; Smreczak, Bozena; Ukalska-Jaruga, Aleksandra

2017-04-01

The level of 16PAH accumulation was determined in 75 soil samples collected from two agricultural regions of Poland corresponding to the smallest Polish administrative unit at the LAU 2 level. Both regions are characterised by similar territory and soil cover but different history of pollution and different pressure of anthropogenic factors. Overall accumulation of Σ16PAHs in the upper soil layer was within a wide range with the median value of 291 and 1253 μg kg -1 for a non-contaminated and high anthropopressure region, respectively. Nearly 75 % of the total polycyclic aromatic hydrocarbon (PAH) pool was represented by high molecular four-to-six-ring compounds, deriving mainly from combustion sources. The total organic carbon (C org ) and black carbon (BC) contents were the main parameters associated with the PAH accumulation in soils, and the level of the regional anthropopressure was considered a significant factor. The strongest links of PAHs/BC (r = 0.70, p ≤ 0.05) were found in the region of high anthropopressure, characterized by a relatively high content of BC (up to 45.3 g kg -1 ), which tends to heavily adsorb hydrocarbons. In a region of low influence exerted by anthropopressure, the PAH/C org or PAH/BC relationships were not observed, which may suggest different diffuse sources of PAH origin and a dominant role of other organic matter fractions in retention of PAHs in soils.

Microbial community composition and PAHs removal potential of indigenous bacteria in oil contaminated sediment of Taean coast, Korea.

PubMed

Lee, Dong Wan; Lee, Hanbyul; Lee, Aslan Hwanhwi; Kwon, Bong-Oh; Khim, Jong Seong; Yim, Un Hyuk; Kim, Beom Seok; Kim, Jae-Jin

2018-03-01

The tidal flats near Sinduri beach in Taean, Korea, have been severely contaminated by heavy crude oils due to the Korea's worst oil spill accident, say the Hebei Spirit Oil Spill, in 2007. Crude oil compounds, including polycyclic aromatic hydrocarbons (PAHs), pose significant environmental damages due to their wide distribution, persistence, high toxicity, mutagenicity, and carcinogenicity. Microbial community of Sinduri beach sediments samples was analyzed by metagenomic data with 16S rRNA gene amplicons. Three phyla (Proteobacteria, Firmicutes, and Bacteroidetes) accounted for approximately ≥93.0% of the total phyla based on metagenomic analysis. Proteobacteria was the dominant phylum in Sinduri beach sediments. Cultivable bacteria were isolated from PAH-enriched cultures, and bacterial diversity was investigated through performing culture characterization followed by molecular biology methods. Sixty-seven isolates were obtained, comprising representatives of Actinobacteria, Firmicutes, α- and γ-Proteobacteria, and Bacteroidetes. PAH catabolism genes, such as naphthalene dioxygenase (NDO) and aromatic ring hydroxylating dioxygenase (ARHDO), were used as genetic markers to assess biodegradation of PAHs in the cultivable bacteria. The ability to degrade PAHs was demonstrated by monitoring the removal of PAHs using a gas chromatography mass spectrometer. Overall, various PAH-degrading bacteria were widely present in Sinduri beach sediments and generally reflected the restored microbial community. Among them, Cobetia marina, Rhodococcus soli, and Pseudoalteromonas agarivorans were found to be significant in degradation of PAHs. This large collection of PAH-degrading strains represents a valuable resource for studies investigating mechanisms of PAH degradation and bioremediation in oil contaminated coastal environment, elsewhere. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Characterization of PAHs in fly ashes from coke production].

PubMed

Mu, Ling; Peng, Lin; Liu, Xiao-Feng; Bai, Hui-Ling; Zhang, Jian-Qiang

2013-03-01

In order to investigate the characteristics of polycyclic aromatic hydrocarbons (PAHs) in ashes from coking, PAHs in ashes from three coke production plants were analyzed with GC-MS, and the distribution characteristics of PAHs and potential toxicity risk were discussed. The sum of 16 EPA prior PAHs varied from 8.17 x 10(2) to 5.17 x 10(3) microg x g(-1). PAH contents from the coke oven (stamp charging) with the height of 3.2 m were two times higher than those from the one (top charging) with the height of 6.0 m, and PAHs in ashes from coal charging were significantly higher than those from coke pushing in the same plant. Four-ring and five-ring PAHs were the dominant species in ashes from coking and the sum of them accounted for more than 80.00% of total PAHs. Chrysene (Chr), benzo [a] anthracene (BaA) and benzo [b] fluoranthene (BbF) were abundant in all ash samples. The content of total BaP-based toxic equivalency (BaPeq) ranged from 1.64 x 10(2) to 9.57 x 10(2) microg x g(-1). From the carcinogenic point of view, besides benzo [a] pyrene (BaP), dibenz [a,h] anthracene (DbA) contributed most to the overall toxicity of PAHs, followed by BaA and BbF. BaPeq concentration from coal charging was 5.21-fold higher than that from coke pushing, indicating that different reuse ways should be considered based on their specific toxicity profiles of PAHs.

Urbanization-related changes in soil PAHs and potential health risks of emission sources in a township in Southern Jiangsu, China.

PubMed

Cao, Hongbin; Chao, Sihong; Qiao, Li; Jiang, Yanxue; Zeng, Xiancai; Fan, Xiaoting

2017-01-01

Urbanization, which is characterized by population aggregation, industrial development, and increased traffic load, may change local polycyclic aromatic hydrocarbons (PAH) emissions and their associated health risks. To investigate these changes, we collected soil samples in 2009 and 2014 in a rapidly developing small town in Southern Jiangsu (China) and measured the concentrations of 16 PAHs via gas chromatography-mass spectrometry. Although the total PAHs decreased from 4586.6 to 640.6ng/g, the concentrations of the high-molecular-weight PAHs benzo(b)fluoranthene and benzo(a)pyrene increased due to changes in the PAH sources. Source apportionment by positive matrix factorization indicated that the two sources responsible for the highest soil PAH contributions changed from biomass combustion (42%) and coal combustion (32%) in 2009 to coal, biomass and natural gas combustion (35%) and diesel combustion (33%) in 2014. However, the two sources with the highest associated health risks were diesel and gasoline combustion in both years. The incremental lifetime cancer risk for residents exposed to PAHs in the soil via incidental ingestion and dermal contact decreased from 1.75×10 -6 to 1.60×10 -6 . The ban on open burning of straw and the substitution of coal with natural gas offset the PAH health risks due to increased urbanization. Copyright © 2016 Elsevier B.V. All rights reserved.

First results from the oil sands passive air monitoring network for polycyclic aromatic compounds.

PubMed

Schuster, Jasmin K; Harner, Tom; Su, Ky; Mihele, Cristian; Eng, Anita

2015-03-03

Results are reported from an ongoing passive air monitoring study for polycyclic aromatic compounds (PACs) in the Athabasca oil sands region in Alberta, Canada. Polyurethane foam (PUF) disk passive air samplers were deployed for consecutive 2-month periods from November 2010 to June 2012 at 17 sites. Samples were analyzed for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, dibenzothiophene and its alkylated derivatives (DBTs). Relative to parent PAHs, alkylated PAHs and DBTs are enriched in bitumen and therefore considered to be petrogenic markers. Concentrations in air were in the range 0.03-210 ng/m(3), 0.15-230 ng/m(3) and 0.01-61 ng/m(3) for ∑PAHs, ∑alkylated PAHs and ΣDBTs, respectively. An exponential decline of the PAC concentrations in air with distance from mining areas and related petrogenic sources was observed. The most significant exponential declines were for the alkylated PAHs and DBTs and attributed to their association with mining-related emissions and near-source deposition, due to their lower volatility and greater association with depositing particles. Seasonal trends in concentrations in air for PACs were not observed for any of the compound classes. However, a forest fire episode during April to July 2011 resulted in greatly elevated PAH levels at all passive sampling locations. Alkylated PAHs and DBTs were not elevated during the forest fire period, supporting their association with petrogenic sources. Based on the results of this study, an "Athabasca PAC profile" is proposed as a potential source marker for the oil sands region. The profile is characterized by ∑PAHs/∑Alkylated PAHs = ∼0.2 and ∑PAHs/∑DBTs = ∼5.

Polycyclic aromatic hydrocarbons and their molecular diagnostic ratios in urban atmospheric respirable particulate matter

NASA Astrophysics Data System (ADS)

del Rosario Sienra, María; Rosazza, Nelson G.; Préndez, Margarita

2005-06-01

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) in Santiago de Chile city were evaluated to study particulate PAHs profiles during cold and spring weather periods. Urban atmospheric particulate matter PM10 was collected using High Volume PM10 samplers. Fifteen samples of 24 h during austral winter and 20 samples of 24 h during spring, 2000 were collected at two sampling sites (North-East and Central areas of the city) whose characteristics were representative of the prevailing conditions. Seventeen PAHs were quantified and total PAHs concentration ranged from 1.39 to 59.98 ng m -3, with a seasonal variation (winter vs. spring ratio) from 0.5 to 12.6 ng m -3. Molecular diagnostic ratios were used to characterize and identify PAHs emission sources such as combustion and biogenic emissions. Results showed that the major sources of respirable organic aerosol PM10 in Santiago are mobile and stationary ones.

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

Bioavailability of polycyclic aromatic hydrocarbons (PAHs) to short-neck clam (Paphia undulata) from sediment matrices in mudflat ecosystem of the west coast of Peninsular Malaysia.

PubMed

Keshavarzifard, Mehrzad; Zakaria, Mohamad Pauzi; Hwai, Tan Shau

2017-06-01

The bioaccumulation and bioavailability of polycyclic aromatic hydrocarbons (PAHs) were characterized in sediment and Paphia undulata (short-neck clam) from six mudflat areas in the west coasts of Peninsular Malaysia. The concentrations of total PAHs varied from 357.1 to 6257.1 and 179.9 ± 7.6 to 1657.5 ± 53.9 ng g -1 dry weight in sediment and short-neck clam samples, respectively. PAHs can be classified as moderate to very high level of pollution in sediments and moderate to high level of pollution in short-neck clams. The diagnostic ratios of individual PAHs and principal component analysis indicate both petrogenic and pyrogenic sources with significant dominance of pyrogenic source. The first PAHs biota-sediment accumulation factors and relative biota-sediment accumulation factors data for short-neck clam were obtained in this study, indicating a preferential accumulation of lower molecular weight PAHs. Evaluation of PAH levels in sediments and short-neck clams indicates that short-neck clam could be introduced as a good biomonitor in mudflats. The results also demonstrated that under environmental conditions, the sedimentary load of hydrocarbons appears to be one of the factors controlling their bioavailability to biota.

BMP type II receptor as a therapeutic target in pulmonary arterial hypertension.

PubMed

Orriols, Mar; Gomez-Puerto, Maria Catalina; Ten Dijke, Peter

2017-08-01

Pulmonary arterial hypertension (PAH) is a chronic disease characterized by a progressive elevation in mean pulmonary arterial pressure. This occurs due to abnormal remodeling of small peripheral lung vasculature resulting in progressive occlusion of the artery lumen that eventually causes right heart failure and death. The most common cause of PAH is inactivating mutations in the gene encoding a bone morphogenetic protein type II receptor (BMPRII). Current therapeutic options for PAH are limited and focused mainly on reversal of pulmonary vasoconstriction and proliferation of vascular cells. Although these treatments can relieve disease symptoms, PAH remains a progressive lethal disease. Emerging data suggest that restoration of BMPRII signaling in PAH is a promising alternative that could prevent and reverse pulmonary vascular remodeling. Here we will focus on recent advances in rescuing BMPRII expression, function or signaling to prevent and reverse pulmonary vascular remodeling in PAH and its feasibility for clinical translation. Furthermore, we summarize the role of described miRNAs that directly target the BMPR2 gene in blood vessels. We discuss the therapeutic potential and the limitations of promising new approaches to restore BMPRII signaling in PAH patients. Different mutations in BMPR2 and environmental/genetic factors make PAH a heterogeneous disease and it is thus likely that the best approach will be patient-tailored therapies.

PAH Emission from Disks around Intermediate-Mass Stars: The Peculiar Aroma of Hydrocarbons Orbiting Herbig Ae/Be Stars

NASA Astrophysics Data System (ADS)

Keller, L. D.; Sloan, G. C.

2009-12-01

Over half of the intermediate-mass young stellar objects in the Galaxy (e.g. Herbig Ae/Be stars or HAeBe) have high-contrast emission in the mid-infrared spectral features of polycyclic aromatic hydrocarbons (PAHs) above the continuum produced by thermal emission from dust in the circumstellar disks. We have examined the PAH emission in detail for 30 HAeBe stars observed with the Spitzer IRS. We have identified some trends that, should they survive in a larger sample of HAeBe stars, will allow us to infer large-scale disk geometry (both inner and outer) and the degree of photo-processing of organic molecular material in HAeBe disks: HAeBe stars apparently have distinctive PAH spectra among the many other astronomical environments that are characterized by strong PAH emission; strong PAH emission is not necessarily an indicator of a particular disk geometry; PAH spectra of HAeBe stars change systematically with stellar effective temperature; PAH in HAeBe disks are ionized. As part of a Spitzer archival project we are applying our spectral analysis methods to an even larger sample of HAeBe stars observed with the IRS and currently available in the Spitzer archive. Here we report preliminary results as we begin the larger study.

Role for miR-204 in human pulmonary arterial hypertension

PubMed Central

Courboulin, Audrey; Paulin, Roxane; Giguère, Nellie J.; Saksouk, Nehmé; Perreault, Tanya; Meloche, Jolyane; Paquet, Eric R.; Biardel, Sabrina; Provencher, Steeve; Côté, Jacques; Simard, Martin J.

2011-01-01

Pulmonary arterial hypertension (PAH) is characterized by enhanced proliferation and reduced apoptosis of pulmonary artery smooth muscle cells (PASMCs). Because microRNAs have been recently implicated in the regulation of cell proliferation and apoptosis, we hypothesized that these regulatory molecules might be implicated in the etiology of PAH. In this study, we show that miR-204 expression in PASMCs is down-regulated in both human and rodent PAH. miR-204 down-regulation correlates with PAH severity and accounts for the proliferative and antiapoptotic phenotypes of PAH-PASMCs. STAT3 activation suppresses miR-204 expression, and miR-204 directly targets SHP2 expression, thereby SHP2 up-regulation, by miR-204 down-regulation, activates the Src kinase and nuclear factor of activated T cells (NFAT). STAT3 also directly induces NFATc2 expression. NFAT and SHP2 were needed to sustain PAH-PASMC proliferation and resistance to apoptosis. Finally, delivery of synthetic miR-204 to the lungs of animals with PAH significantly reduced disease severity. This study uncovers a new regulatory pathway involving miR-204 that is critical to the etiology of PAH and indicates that reestablishing miR-204 expression should be explored as a potential new therapy for this disease. PMID:21321078

Relationship between the water-exchangeable fraction of PAH and the organic matter composition of sediments.

PubMed

Belles, Angel; Alary, Claire; Mamindy-Pajany, Yannick; Abriak, Nor-Edine

2016-12-01

The sorption of PAH on 12 different sediments was investigated and was correlated to their corresponding organic matter (OM) content and quality. For this purpose, the OM was precisely characterized using thermal analysis consisting in the successive combustion and quantification of the increasingly thermostable fractions of the OM. Simultaneously, the water-exchangeable fraction of the sorbed PAH defined as the amount of PAH freely exchanged between the water and the sediment (by opposition to the PAH harshly sorbed to the sediments particles) was determined using a passive sampler methodology recently developed. The water concentrations, when the sediment-water system is equilibrated, were also assessed which allows the determination of the sediment-water distribution coefficients without artifacts introduced by the non water-exchangeable fraction of PAH. Hence, the present study provides the distribution coefficients of PAH between the water and 4 different OM fractions combusted at a specific temperature range. The calculated distribution coefficients demonstrate that the sedimentary OM combusted at the intermediate temperature range (between 300 °C and 450 °C) drives the reversible sorption of PAH while the inferred sorption to the OM combusted at a lower and higher temperature range does not dominate the partitioning process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Real-time characterization of particle-bound polycyclic aromatic hydrocarbons in ambient aerosols and from motor-vehicle exhaust

NASA Astrophysics Data System (ADS)

Polidori, A.; Hu, S.; Biswas, S.; Delfino, R. J.; Sioutas, C.

2007-12-01

A photo-electric aerosol sensor, a diffusion charger, an Aethalometer, and a continuous particle counter were used along with other real-time instruments to characterize the particle-bound polycyclic aromatic hydrocarbon (p-PAH) content, and the physical/chemical characteristics of aerosols collected a) in Wilmington (CA) near the Los Angeles port and close to 2 major freeways, and b) at a dynamometer testing facility in downtown Los Angeles (CA), where 3 diesel trucks were tested. In Wilmington, the p-PAH, surface area, particle number, and "black" carbon concentrations were 4-8 times higher at 09:00-11:00 a.m. than between 17:00 and 18:00 p.m., suggesting that during rush hour traffic people living in that area are exposed to a higher number of diesel combustion particles enriched in p-PAH coatings. Dynamometer tests revealed that the p-PAH emissions from the "baseline" truck (no catalytic converted) were up to 200 times higher than those from the 2 vehicles equipped with advanced emission control technologies, and increased when the truck was accelerating. In Wilmington, integrated filter samples were collected and analyzed to determine the concentrations of the most abundant p-PAHs. A correlation between the total p-PAH concentration (μg/m3) and the measured photo-electric aerosol sensor signal (fA) was also established. Estimated ambient p-PAH concentrations (Average = 0.64 ng/m3; Standard deviation = 0.46 ng/m3) were in good agreement with those reported in previous studies conducted in Los Angeles during a similar time period. Finally, we calculated the approximate theoretical lifetime (70 years per 24-h/day) lung-cancer risk in the Wilmington area due to inhalation of multi-component p-PAHs and "black" carbon. Our results indicate that the lung-cancer risk is highest during rush hour traffic and lowest in the afternoon, and that the genotoxic risk of the considered p-PAHs does not seem to contribute to a significant part of the total lung-cancer risk attributable to "black" carbon.

Real-time characterization of particle-bound polycyclic aromatic hydrocarbons in ambient aerosols and from motor-vehicle exhaust

NASA Astrophysics Data System (ADS)

Polidori, A.; Hu, S.; Biswas, S.; Delfino, R. J.; Sioutas, C.

2008-03-01

A photo-electric aerosol sensor, a diffusion charger, an Aethalometer, and a continuous particle counter were used along with other real-time instruments to characterize the particle-bound polycyclic aromatic hydrocarbon (p-PAH) content, and the physical/chemical characteristics of aerosols collected a) in Wilmington (CA) near the Los Angeles port and close to 2 major freeways, and b) at a dynamometer testing facility in downtown Los Angeles (CA), where 3 diesel trucks were tested. In Wilmington, the p-PAH, surface area, particle number, and "black" carbon concentrations were 4-8 times higher at 09:00-11:00 a.m. than between 17:00 and 18:00 p.m., suggesting that during rush hour traffic people living in that area are exposed to a higher number of diesel combustion particles enriched in p-PAH coatings. Dynamometer tests revealed that the p-PAH emissions from the "baseline" truck (no catalytic converter) were up to 200 times higher than those from the 2 vehicles equipped with advanced emission control technologies, and increased when the truck was accelerating. In Wilmington, integrated filter samples were collected and analyzed to determine the concentrations of the most abundant p-PAHs. A correlation between the total p-PAH concentration (μg/m3) and the measured photo-electric aerosol sensor signal (fA) was also established. Estimated ambient p-PAH concentrations (Average=0.64 ng/m3; Standard deviation=0.46 ng/m3 were in good agreement with those reported in previous studies conducted in Los Angeles during a similar time period. Finally, we calculated the approximate theoretical lifetime (70 years per 24-h/day) lung-cancer risk in the Wilmington area due to inhalation of multi-component p-PAHs and "black" carbon. Our results indicate that the lung-cancer risk is highest during rush hour traffic and lowest in the afternoon, and that the genotoxic risk of the considered p-PAHs does not seem to contribute to a significant part of the total lung-cancer risk attributable to "black" carbon.

Pulmonary arterial hypertension associated with chronic active Epstein-Barr virus infection.

PubMed

Fukuda, Yutaka; Momoi, Nobuo; Akaihata, Mitsuko; Nagasawa, Katsutoshi; Mitomo, Masaki; Aoyagi, Yoshimichi; Endoh, Kisei; Hosoya, Mitsuaki

2015-08-01

Chronic active Epstein-Barr virus (EBV) infection (CAEBV), characterized by persistent infectious mononucleosis-like symptoms, can lead to cardiovascular complications including coronary artery aneurysm or myocarditis. Here, we present the case of an 11-year-old boy with pulmonary arterial hypertension (PAH) and junctional ectopic tachycardia associated with CAEBV. The patient did not have any major symptoms attributed to CAEBV, such as fever, lymphadenopathy or splenomegaly when the PAH developed. Mild liver dysfunction was found at the first examination, and it persisted. Two years after the PAH symptoms appeared, CAEBV was evident, based on deteriorated liver function, hepatosplenomegaly, and coronary artery aneurysms. CAEBV should be considered as a cause of secondary PAH, particularly when liver dysfunction coexists. © 2015 Japan Pediatric Society.

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.

Testing the association between anomalous microwave emission and PAHs in the diffuse ISM

NASA Astrophysics Data System (ADS)

Berkeley, Matthew R.; Chuss, David; Kogut, Al

2018-01-01

Testing cosmic inflation is currently a primary focus of the Cosmology community. In order to verify the theory and to determine the energy scale of inflation, it is necessary to identify the characteristic B-mode polarization signal in the CMB. This signal, predicted by inflation theory, is expected to be very faint. It is therefore important to accurately characterize and remove foreground polarization components such as thermal dust and synchrotron emission.Some of these components have already been accurately characterized, but there are others that are not so well understood. In 1996, a new galactic foreground emission component was discovered. Dubbed 'anomalous microwave emission' (AME), this new foreground has yet to be identified. Though its physical origin remains uncertain, the leading hypothesis for the origin of this foreground proposes that the emission comes from rapidly rotating small dust grains called Polycyclic Aromatic Hydrocarbons (PAHs), or 'spinning dust'. PAHs are a family of hydrocarbon molecules with characteristic bending and stretching modes that have identifiable emission spectra in the mid-infrared region. The Wide-field Infrared Survey Explorer (WISE) is a satellite that was launched in 2010 into a polar orbit, enabling it to take images of the entire sky at four different mid-infrared wavelengths. These wavelengths cover the spectral region with the aforementioned PAH emission features in the mid-infrared. WISE archival data therefore makes it possible to construct a full-sky map of PAH emission.We present full sky maps using WISE data as a preliminary result towards creating a full sky PAH map.

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.

Paradoxical Adipose Hyperplasia and Cellular Effects After Cryolipolysis: A Case Report.

PubMed

Seaman, Scott A; Tannan, Shruti C; Cao, Yiqi; Peirce, Shayn M; Gampper, Thomas J

2016-01-01

Cryolipolysis is a noninvasive technique for the reduction of subcutaneous adipose tissue by controlled, localized cooling, causing adipocyte apoptosis, reportedly without affecting surrounding tissue. Although cryolipolysis has a low incidence of adverse side effects 33 cases of paradoxical adipose hyperplasia (PAH) have been reported and the precise pathogenesis of PAH is poorly understood. This present case study of PAH aims to characterize the pathological changes in the adipose tissue of PAH on a cellular level by using multiple different assays [hematoxy lin and eosin staining, LIVE/DEAD staining, BODIPY(®) 558/568 C12 (4,4-Difluoro-5-(2-Thienyl)-4-Bora-3a,4a-Diaza-s-Indacene-3-dodecanoic acid) staining]. to identify the underlying mechanism of PAH and reduce the prevalence of PAH in the future. Tissue with PAH had fewer viable cells, significantly decreased quantities of interstitial cells (p = 0.04), and fewer vessels per adipose tissue area when compared to the control tissue. Adipocytes from the PAH tissue were on average slightly smaller than the control adipocytes. Adipocytes of PAH tissue had irregularly contoured edges when compared to the smooth, round edges of the control tissue. These findings from a neutral third party are contrary to prior reports from the inventors of this technique regarding effects of cryolipolysis on both the microvasculature and interstitial cells in adipose tissue. Our use of different assays to compare cryolipolysis-treated PAH tissue with untreated adipose tissue in the same patient showed adipose tissue that developed PAH was hypocellular and hypovascular. Contrary to prior reports from the inventors, cryolipolysis may cause vessel loss, which could lead to ischemia and/or hypoxia that further contributes to adipocyte death. LEVEL OF EVIDENCE 5: Risk. © 2015 The American Society for Aesthetic Plastic Surgery, Inc. Reprints and permission: journals.permissions@oup.com.

pH-responsive charge-reversal polymer-functionalized boron nitride nanospheres for intracellular doxorubicin delivery

PubMed Central

Feng, Shini; Zhi, Chunyi; Gao, Xiao-Dong

2018-01-01

Background Anticancer drug-delivery systems (DDSs) capable of responding to the physiological stimuli and efficiently releasing drugs inside tumor cells are highly desirable for effective cancer therapy. Herein, pH-responsive, charge-reversal poly(allylamine hydrochlorid)−citraconic anhydride (PAH-cit) functionalized boron nitride nanospheres (BNNS) were fabricated and used as a carrier for the delivery and controlled release of doxorubicin (DOX) into cancer cells. Methods BNNS was synthesized through a chemical vapor deposition method and then functionalized with synthesized charge-reversal PAH-cit polymer. DOX@PAH-cit–BNNS complexes were prepared via step-by-step electrostatic interactions and were fully characterized. The cellular uptake of DOX@PAH-cit–BNNS complexes and DOX release inside cancer cells were visualized by confocal laser scanning microscopy. The in vitro anticancer activity of DOX@ PAH-cit–BNNS was examined using CCK-8 and live/dead viability/cytotoxicity assay. Results The PAH-cit–BNNS complexes were nontoxic to normal and cancer cells up to a concentration of 100 µg/mL. DOX was loaded on PAH-cit–BNNS complexes with high efficiency. In a neutral environment, the DOX@PAH-cit–BNNS was stable, whereas the loaded DOX was effectively released from these complexes at low pH condition due to amide hydrolysis of PAH-cit. Enhanced cellular uptake of DOX@PAH-cit–BNNS complexes and DOX release in the nucleus of cancer cells were revealed by confocal microscopy. Additionally, the effective delivery and release of DOX into the nucleus of cancer cells led to high therapeutic efficiency. Conclusion Our findings indicated that the newly developed PAH-cit–BNNS complexes are promising as an efficient pH-responsive DDS for cancer therapy. PMID:29440891

PAH determination based on a rapid and novel gas purge-microsyringe extraction (GP-MSE) technique in road dust of Shanghai, China: Characterization, source apportionment, and health risk assessment.

PubMed

Zheng, Xin; Yang, Yi; Liu, Min; Yu, Yingpeng; Zhou, John L; Li, Donghao

2016-07-01

A novel cleanup technique termed as gas purge-microsyringe extraction (GP-MSE) was evaluated and applied for polycyclic aromatic hydrocarbon (PAH) determination in road dust samples. A total of 68 road dust samples covering almost the entire Shanghai area were analyzed for 16 priority PAHs using gas chromatography-mass spectrometry. The results indicate that the total PAH concentrations over the investigated sites ranged from 1.04μg/g to 134.02μg/g dw with an average of 13.84μg/g. High-molecular-weight compounds (4-6 rings PAHs) were significantly dominant in the total mass of PAHs, and accounted for 77.85% to 93.62%. Diagnostic ratio analysis showed that the road dust PAHs were mainly from the mixture of petroleum and biomass/coal combustions. Principal component analysis in conjunction with multiple linear regression indicated that the two major origins of road dust PAHs were vehicular emissions and biomass/fossil fuel combustions, which contributed 66.7% and 18.8% to the total road dust PAH burden, respectively. The concentration of benzo[a]pyrene equivalent (BaPeq) varied from 0.16μg/g to 24.47μg/g. The six highly carcinogenic PAH species (benz(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, dibenz(a,h)anthracene, and indeno(1,2,3-cd)pyrene) accounted for 98.57% of the total BaPeq concentration. Thus, the toxicity of PAHs in road dust was highly associated with high-molecular-weight compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

Polycyclic aromatic hydrocarbon in urban soils of an Eastern European megalopolis: distribution, source identification and cancer risk evaluation

NASA Astrophysics Data System (ADS)

Shamilishvily, George; Abakumov, Evgeny; Gabov, Dmitriy

2018-05-01

This study explores qualitative and quantitative composition of 15 priority polycyclic aromatic hydrocarbons (PAHs) in urban soils of some parkland, residential and industrial areas of the large industrial centre of Saint Petersburg (Russian Federation) in Eastern Europe. The aim of the study was to test the hypothesis on the PAH loading differences among urban territories with different land use scenarios. Benzo(a)pyrene toxic equivalency factors (TEFs) were used to calculate BaPeq in order to evaluate carcinogenic risk of soil contamination with PAHs. Results of the study demonstrated that soils within residential and industrial areas are characterized by common loads of PAHs generally attributed to high traffic activity in the city. Considerable levels of soil contamination with PAHs were noted. Total PAH concentrations ranged from 0.33 to 8.10 mg kg-1. A larger portion of high-molecular-weight PAHs along with determined molecular ratios suggest the predominance of pyrogenic sources, mainly attributed to combustion of gasoline, diesel and oil. Petrogenic sources of PAHs have a significant portion and define the predominance of low-molecular-weight PAHs associated with petroleum, such as phenanthrene. Derived concentrations of seven carcinogenic PAHs as well as calculated BaPeq were multiple times higher than reported in a number of other studies. The obtained BaPeq concentrations of the sum of 15 PAHs ranged from 0.05 to 1.39 mg kg-1. A vast majority of examined samples showed concentrations above the safe value of 0.6 mg kg-1 (CCME, 2010). However, estimated incremental lifetime risks posed to the population through distinct routes of exposure were in an acceptable range. One-way ANOVA results showed significant differences in total PAHs and the sum of seven carcinogenic PAH concentrations as well as in levels of FLU, PHE, FLT, PYR, BaA, CHR, BbF, BaP and BPE among parkland, residential and industrial land uses, suggesting the influence of the land use factor.

Characterization of EPA's 16 priority pollutant polycyclic aromatic hydrocarbons (PAHs) in tank bottom solids and associated contaminated soils at oil exploration and production sites in Texas.

PubMed

Bojes, Heidi K; Pope, Peter G

2007-04-01

The purpose of this study was to determine the concentration and types of polycyclic aromatic hydrocarbons (PAHs), a group of environmentally toxic and persistent chemicals, at contaminated oil exploration and production (E&P) sites located in environmentally sensitive and geographically distinct areas throughout Texas. Samples of tank bottom solids, the oily sediment that collects at the bottom of the tanks, were collected from inactive crude oil storage tanks at E&P sites and hydrocarbon contaminated soil samples were collected from the area surrounding each tank that was sampled. All samples were analyzed for the 16 PAH priority pollutant listed by US EPA and for total petroleum hydrocarbons (TPH). The results demonstrate that overall average PAH concentrations were significantly higher in tank bottom solids than in contaminated soils. Total PAH concentrations decreased predictably with diminishing hydrocarbon concentrations; but the percent fraction of carcinogenic PAHs per total measured PAH content increased from approximately 12% in tank bottom solids to about 46% in the contaminated soils. These results suggest that the PAH content found in tank bottom solids cannot reliably be used to predict the PAH content in associated contaminated soil. Comparison of PAHs to conservative risk-based screening levels for direct exposure to soil and leaching from soil to groundwater indicate that PAHs are not likely to exceed default risk-based thresholds in soils containing TPH of 1% (10,000mg/kg) or less. These results show that the magnitude of TPH concentration may be a useful indicator of potential risk from PAHs in crude oil-contaminated soils. The results also provide credibility to the 1% (10,000mg/kg) TPH cleanup level, used in Texas as a default management level at E&P sites located in non-sensitive areas, with respect to PAH toxicity.

Urban rivers as conveyors of hydrocarbons to sediments of estuarine areas: source characterization, flow rates and mass accumulation.

PubMed

Mauad, Cristiane R; Wagener, Angela de L R; Massone, Carlos G; Aniceto, Mayara da S; Lazzari, Letícia; Carreira, Renato S; Farias, Cássia de O

2015-02-15

Aliphatic (n-C12-n-C40, unresolved complex mixture, resolved peaks) and aromatic hydrocarbons (46 PAH) were investigated in suspended particulate matter (SPM) sampled over eleven months in six of the major rivers and two channels of the Guanabara Bay Basin. PAH flow rates of the most contaminated rivers, the contribution to the PAH sediment load of the receiving bay, and the main sources of hydrocarbons were determined. PAH (38) ranged from 28 ng L(-1) to 11,514 ng L(-1). Hydrocarbon typology and statistical evaluation demonstrated contribution of distinct sources in different regions and allowed quantification of these contributions. Total flow rate for the five major rivers amounts to 3 t year(-1) and responds for 30% of the total PAH annual input into the northern area of the Guanabara Bay. For the first time PAH mass deposited in the bay sediments has been estimated and shall serve as base for decision making and source abatement. Copyright © 2014 Elsevier B.V. All rights reserved.

An Organic Geochemical Assessment of CO2-Coal Interactions During Sequestration

USGS Publications Warehouse

Kolak, Jonathan J.; Burruss, Robert A.

2003-01-01

Three well-characterized coal samples of varying rank were extracted with supercritical CO2 to determine the amount of polycyclic aromatic hydrocarbons (PAHs) that could be mobilized during simulated CO2 injection/sequestration in deep coal beds. The supercritical CO2 extractions were conducted at 40?C and 100 bars, roughly corresponding to a depth of 1 km. The greatest amount of PAHs was extracted from the high-volatile C bituminous coal sample. Extracts from the subbituminous C and anthracite coal samples contained lower concentrations of these compounds. The effectiveness of supercritical CO2 in liberating PAHs from the coal sample was evaluated in a comparison with a parallel series of Soxhlet extractions using 100% dichloromethane. More PAHs were extracted from the lower rank coal samples with dichloromethane than with supercritical CO2. The results from this investigation indicate that, regardless of coal rank, CO2 injection into deep coal beds may mobilize PAHs from the coal matrix. However, more PAHs could be mobilized during CO2 sequestration in a high-volatile C bituminous coal bed than in either of the other two coal ranks studied.

Plasma L-arginine levels distinguish pulmonary arterial hypertension from left ventricular systolic dysfunction.

PubMed

Sandqvist, Anna; Schneede, Jörn; Kylhammar, David; Henrohn, Dan; Lundgren, Jakob; Hedeland, Mikael; Bondesson, Ulf; Rådegran, Göran; Wikström, Gerhard

2018-03-01

Pulmonary arterial hypertension (PAH) is a life-threatening condition, characterized by an imbalance of vasoactive substances and remodeling of pulmonary vasculature. Nitric oxide, formed from L-arginine, is essential for homeostasis and smooth muscle cell relaxation in PAH. Our aim was to compare plasma concentrations of L-arginine, asymmetric dimethylarginine (ADMA), and symmetric dimethylarginine (SDMA) in PAH compared to left ventricular systolic dysfunction (LVSD) and healthy subjects. This was an observational, multicenter study comparing 21 patients with PAH to 14 patients with LVSD and 27 healthy subjects. Physical examinations were obtained and blood samples were collected. Plasma levels of ADMA, SDMA, L-arginine, L-ornithine, and L-citrulline were analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Plasma levels of ADMA and SDMA were higher, whereas L-arginine and L-arginine/ADMA ratio were lower in PAH patients compared to healthy subjects (p < 0.001). Patients with PAH also had lower levels of L-arginine than patients with LVSD (p < 0.05). L-Arginine correlated to 6 min walking distance (6MWD) (r s  = 0.58, p = 0.006) and L-arginine/ADMA correlated to WHO functional class (r s  = -0.46, p = 0.043) in PAH. In conclusion, L-arginine levels were significantly lower in treatment naïve PAH patients compared to patients with LVSD. Furthermore, L-arginine correlated with 6MWD in PAH. L-arginine may provide useful information in differentiating PAH from LVSD.

Transboundary movement of polycyclic aromatic hydrocarbons (PAHs) in the Kuroshio Sphere of the western Pacific Ocean

NASA Astrophysics Data System (ADS)

Huang, Hu-Ching; Lee, Chon-Lin; Lai, Chin-Hsing; Fang, Meng-Der; Lai, I.-Chien

2012-07-01

Atmospheric PAHs in the Kuroshio Sphere of southern Taiwan were measured and characterized using samples collected simultaneously at four sites from February to October in 2007. Higher PAH concentrations occurred in winter (range 2.41 ± 1.85 to 40.8 ± 6.97 ng m-3) and autumn (range 1.21 ± 0.32 to 65.1 ± 57.4 ng m-3) than in summer (range 0.87 ± 0.36 to 17.7 ± 2.88 ng m-3). Comparison of the total PAH concentrations from the four sampling sites showed that the total PAH concentrations from the Kaohsiung urban site (KHU) were 1.7-4.4 times higher than those from the Kaohsiung coastal site (KHC), 3.6-26 times those from a rural coastal site (Kenting, KT), and 16.9-53.8 times those from an offshore island site (Lanyu, LY). The PAH compositional pattern, diagnostic ratios and principal component analysis indicated that the major sources of PAHs in the study area can be classified into three categories. The first is vehicular sources from local traffic, the second is natural soils, and the third is industrial activities including coke ovens and incinerator emissions. The results from back trajectories also demonstrated that atmospheric PAHs were produced by local sources but were also influenced by transboundary movement of terrestrial pollutants. The characteristics and sources of atmospheric PAHs identified in this study provide useful information for estimating the effects and transportation of PAHs in the Kuroshio Sphere.

Elevation of Plasma Cell-Free Hemoglobin in Pulmonary Arterial Hypertension

PubMed Central

Janz, David R.; Austin, Eric D.; Bastarache, Julie A.; Wheeler, Lisa A.; Ware, Lorraine B.; Hemnes, Anna R.

2014-01-01

BACKGROUND: Cell-free hemoglobin (CFH) is a potent nitric oxide scavenger associated with poor outcomes in several diseases. Pulmonary arterial hypertension (PAH) is characterized by reduced nitric oxide availability. We hypothesized that CFH would be elevated in PAH and would associate with hemodynamics and clinical outcomes. METHODS: We measured CFH in 200 consecutively evaluated patients with PAH, 16 unaffected bone morphogenetic receptor protein type 2 (BMPR2) mutation carriers, 19 healthy subjects, and 29 patients with pulmonary venous hypertension (PVH). CFH values were tested for association with hemodynamics, time to hospitalization, and death. RESULTS: CFH was elevated in patients with PAH and BMPR2 carriers compared with healthy subjects and patients with PVH (P ≤ .01 all comparisons). There were no differences in CFH across PAH subtypes. CFH modestly correlated with mean pulmonary artery pressure (ρ = 0.16, P = .03) and pulmonary vascular resistance (ρ = 0.21, P = .01) and inversely with cardiac index (ρ = −0.18, P = .02) in patients with PAH. CFH was not associated with hemodynamic response to nitric oxide or death. Patients with the highest CFH levels had increased risk of PAH-related hospitalization when adjusted for age, sex, and PAH cause (hazard ratio, 1.69; 95% CI ,1.08-2.66; P = .02). CONCLUSIONS: CFH is elevated in patients with PAH and BMPR2 carriers compared with healthy subjects and patients with PVH. Elevated CFH levels are independently associated with an increased risk of hospitalization. Further study is required to understand the mechanism of CFH elevation and the potential pathologic contribution of CFH in PAH. PMID:24945582

A proposed procedure for derivation of regulatory values for carcinogenic airborne polycyclic aromatic hydrocarbons (PAHs) based on coal tar pitch (CTP) volatiles.

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

Foureman, G.L.; Smith, R.L.

A procedure for estimating upper bound lifetime human cancer risk from air levels of six common carcinogenic polycyclic aromatic hydrocarbons (PAHs), termed APAHs of concern, is proposed. These PAHs are benzo(a)pyrene, benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, indeno(1,2,3-c,d)pyrene, and chrysene. In application, this proposed procedure would regard any given air level obtained for a APAH of concern to originate from a standard mixture of coal tar pitch (CTP). The given air level for the APAHs of concern is then related to a corresponding air level of CTP and thence, to an inhalation unit cancer risk calculated for CTP. Reference values for the proceduremore » are the relative and absolute PAH composition of a CTP standard (SRM-1597) and the inhalation unit cancer risk. Qualitative characterization of the results are a vital part of the procedure especially when more than one APAH of concern{at} is being considered. Toxic equivalency factors (TEFs) may be used as an evaluative tool in characterization of the procedure and outcome. Limitations of this proposed procedure include the uneven database for the reference values and the inability to consider air samples inclusive of another common carcinogenic PAH, dibenz(a,h)anthracene, due to its lack of documentation in CTP and high TEF« less

Watershed-based sources of polycyclic aromatic hydrocarbons in urban storm water.

PubMed

Stein, Eric D; Tiefenthaler, Liesl L; Schiff, Kenneth

2006-02-01

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic and mutagenic compounds, ubiquitous in the air and water of urban environments, and have been shown to accumulate in coastal estuarine and marine sediments. Although previous studies have documented concentrations and loads of PAHs in urban runoff, little is known about the sources and temporal patterns of PAH loading from storm water. This study characterized the sources and temporal patterns of PAHs in urban storm water by analyzing PAH concentrations and loads from a range of homogeneous land use sites and in-river mass emission sites throughout the greater Los Angeles, California, USA, region. Samples were collected at 30- to 60-min intervals over the course of a storm during multiple storm events over a four-year period in order to investigate PAH sources and inter- and intrastorm patterns in loading. Polycyclic aromatic hydrocarbon storm fluxes ranged from 1.3 g/km2 for the largely undeveloped Arroyo Sequit watershed to 223.7 g/km2 for the highly urbanized Verdugo Wash watershed, with average storm fluxes being 46 times higher in developed versus undeveloped watersheds. Early-season storms repeatedly produced substantially higher loads than comparably sized late-season storms. Within individual storms, PAHs exhibited a moderate first flush with between 30 and 60% of the total PAH load being discharged in the first 20% of the storm volume. The relative distribution of individual PAHs demonstrated a consistent predominance of high-molecular-weight compounds indicative of pyrogenic sources.

Physical and chemical characterization of waste wood derived biochars.

PubMed

Yargicoglu, Erin N; Sadasivam, Bala Yamini; Reddy, Krishna R; Spokas, Kurt

2015-02-01

Biochar, a solid byproduct generated during waste biomass pyrolysis or gasification in the absence (or near-absence) of oxygen, has recently garnered interest for both agricultural and environmental management purposes owing to its unique physicochemical properties. Favorable properties of biochar include its high surface area and porosity, and ability to adsorb a variety of compounds, including nutrients, organic contaminants, and some gases. Physical and chemical properties of biochars are dictated by the feedstock and production processes (pyrolysis or gasification temperature, conversion technology and pre- and post-treatment processes, if any), which vary widely across commercially produced biochars. In this study, several commercially available biochars derived from waste wood are characterized for physical and chemical properties that can signify their relevant environmental applications. Parameters characterized include: physical properties (particle size distribution, specific gravity, density, porosity, surface area), hydraulic properties (hydraulic conductivity and water holding capacity), and chemical and electrochemical properties (organic matter and organic carbon contents, pH, oxidation-reduction potential and electrical conductivity, zeta potential, carbon, nitrogen and hydrogen (CHN) elemental composition, polycyclic aromatic hydrocarbons (PAHs), heavy metals, and leachable PAHs and heavy metals). A wide range of fixed carbon (0-47.8%), volatile matter (28-74.1%), and ash contents (1.5-65.7%) were observed among tested biochars. A high variability in surface area (0.1-155.1g/m(2)) and PAH and heavy metal contents of the solid phase among commercially available biochars was also observed (0.7-83 mg kg(-1)), underscoring the importance of pre-screening biochars prior to application. Production conditions appear to dictate PAH content--with the highest PAHs observed in biochar produced via fast pyrolysis and lowest among the gasification-produced biochars. Copyright © 2014 Elsevier Ltd. All rights reserved.

Developmental exposure to a complex PAH mixture causes persistent behavioral effects in naive Fundulus heteroclitus (killifish) but not in a population of PAH-adapted killifish.

PubMed

Brown, D R; Bailey, J M; Oliveri, A N; Levin, E D; Di Giulio, R T

2016-01-01

Acute exposures to some individual polycyclic aromatic hydrocarbons (PAHs) and complex PAH mixtures are known to cause cardiac malformations and edema in the developing fish embryo. However, the heart is not the only organ impacted by developmental PAH exposure. The developing brain is also affected, resulting in lasting behavioral dysfunction. While acute exposures to some PAHs are teratogenically lethal in fish, little is known about the later life consequences of early life, lower dose subteratogenic PAH exposures. We sought to determine and characterize the long-term behavioral consequences of subteratogenic developmental PAH mixture exposure in both naive killifish and PAH-adapted killifish using sediment pore water derived from the Atlantic Wood Industries Superfund Site. Killifish offspring were embryonically treated with two low-level PAH mixture dilutions of Elizabeth River sediment extract (ERSE) (TPAH 5.04 μg/L and 50.4 μg/L) at 24h post fertilization. Following exposure, killifish were raised to larval, juvenile, and adult life stages and subjected to a series of behavioral tests including: a locomotor activity test (4 days post-hatch), a sensorimotor response tap/habituation test (3 months post hatch), and a novel tank diving and exploration test (3months post hatch). Killifish were also monitored for survival at 1, 2, and 5 months over 5-month rearing period. Developmental PAH exposure caused short-term as well as persistent behavioral impairments in naive killifish. In contrast, the PAH-adapted killifish did not show behavioral alterations following PAH exposure. PAH mixture exposure caused increased mortality in reference killifish over time; yet, the PAH-adapted killifish, while demonstrating long-term rearing mortality, had no significant changes in mortality associated with ERSE exposure. This study demonstrated that early embryonic exposure to PAH-contaminated sediment pore water caused long-term locomotor and behavioral alterations in killifish, and that locomotor alterations could be observed in early larval stages. Additionally, our study highlights the resistance to behavioral alterations caused by low-level PAH mixture exposure in the adapted killifish population. Furthermore, this is the first longitudinal behavioral study to use killifish, an environmentally important estuarine teleost fish, and this testing framework can be used for future contaminant assessment. Copyright © 2015 Elsevier Inc. All rights reserved.

Adverse ventricular-ventricular interactions in right ventricular pressure load: Insights from pediatric pulmonary hypertension versus pulmonary stenosis.

PubMed

Driessen, Mieke M P; Hui, Wei; Bijnens, Bart H; Dragulescu, Andreea; Mertens, Luc; Meijboom, Folkert J; Friedberg, Mark K

2016-06-01

Right ventricular (RV) pressure overload has a vastly different clinical course in children with idiopathic pulmonary arterial hypertension (iPAH) than in children with pulmonary stenosis (PS). While RV function is well recognized as a key prognostic factor in iPAH, adverse ventricular-ventricular interactions and LV dysfunction are less well characterized and the pathophysiology is incompletely understood. We compared ventricular-ventricular interactions as hypothesized drivers of biventricular dysfunction in pediatric iPAH versus PS Eighteen iPAH, 16 PS patients and 18 age- and size-matched controls were retrospectively studied. Cardiac cycle events were measured by M-mode and Doppler echocardiography. Measurements were compared between groups using ANOVA with post hoc Dunnet's or ANCOVA including RV systolic pressure (RVSP; iPAH 96.8 ± 25.4 mmHg vs. PS 75.4 ± 18.9 mmHg; P = 0.011) as a covariate. RV-free wall thickening was prolonged in iPAH versus PS, extending beyond pulmonary valve closure (638 ± 76 msec vs. 562 ± 76 msec vs. 473 ± 59 msec controls). LV and RV isovolumetric relaxation were prolonged in iPAH (P < 0.001; LV 102.8 ± 24.1 msec vs. 63.1 ± 13.7 msec; RV 95 [61-165] vs. 28 [0-43]), associated with adverse septal kinetics; characterized by rightward displacement in early systole and leftward displacement in late RV systole (i.e., early LV diastole). Early LV diastolic filling was decreased in iPAH (73 ± 15.9 vs. PS 87.4 ± 14.4 vs. controls 95.8 ± 12.5 cm/sec; P = 0.004). Prolonged RVFW thickening, prolonged RVFW isovolumetric times, and profound septal dyskinesia are associated with interventricular mechanical discoordination and decreased early LV filling in pediatric iPAH much more than PS These adverse mechanics affect systolic and diastolic biventricular efficiency in iPAH and may form the basis for worse clinical outcomes. We used clinically derived data to study the pathophysiology of ventricular-ventricular interactions in right ventricular pressure overload, demonstrating distinct differences between pediatric pulmonary arterial hypertension (iPAH) and pulmonary stenosis (PS). Altered timing of right ventricular free wall contraction and profound septal dyskinesia are associated with interventricular mechanical discoordination and decreased early LV filling in iPAH much more than PS These adverse mechanics affect systolic and diastolic biventricular efficiency, independent of right ventricular systolic pressure. © 2016 The Authors. Physiological Reports published by Wiley Periodicals, Inc. on behalf of the American Physiological Society and The Physiological Society.

Long-term assessment of natural attenuation: statistical approach on soils with aged PAH contamination.

PubMed

Ouvrard, Stéphanie; Chenot, Elodie-Denise; Masfaraud, Jean-François; Schwartz, Christophe

2013-07-01

Natural attenuation processes valorization for PAH-contaminated soil remediation has gained increasing interest from site owners. A misunderstanding of this method and a small amount of data available does not encourage its development. However, monitored natural attenuation (MNA) offers a valuable, cheaper and environmentally friendly alternative to more classical options such as physico-chemical treatments (e.g., chemical oxidation, thermal desorption). The present work proposes the results obtained during a long-term natural attenuation assessment of historically contaminated industrial soils under real climatic conditions. This study was performed after a 10 year natural attenuation period on 60 off-ground lysimeters filled with contaminated soils from different former industrial sites (coking industry, manufactured gas plants) whose initial concentration of PAH varied between 380 and 2,077 mg kg(-1). The analysed parameters included leached water characterization, soil PAH concentrations, evaluation of vegetation cover quality and quantity. Results showed a good efficiency of the PAH dissipation and limited transfer of contaminants to the environment. It also highlighted the importance of the fine soil fractions in controlling PAH reactivity. PAH dissipation through water leaching was limited and did not present a significant risk for the environment. This PAH water concentration appeared however as a good indicator of overall dissipation rate, thereby illustrating the importance of pollutant availability in predicting its degradation potential.

Detoxification of polycyclic aromatic hydrocarbons (PAHs) in Arabidopsis thaliana involves a putative flavonol synthase.

PubMed

Hernández-Vega, Juan C; Cady, Brian; Kayanja, Gilbert; Mauriello, Anthony; Cervantes, Natalie; Gillespie, Andrea; Lavia, Lisa; Trujillo, Joshua; Alkio, Merianne; Colón-Carmona, Adán

2017-01-05

Polycyclic aromatic hydrocarbons (PAHs) are environmental contaminants with cytotoxic, teratogenic and carcinogenic properties. Bioremediation studies with bacteria have led to the identification of dioxygenases (DOXs) in the first step to degrade these recalcitrant compounds. In this study, we characterized the role of the Arabidopsis thaliana AT5G05600, a putative DOX of the flavonol synthase family, in the transformation of PAHs. Phenotypic analysis of loss-of-function mutant lines showed that these plant lines were less sensitive to the toxic effects of phenanthrene, suggesting possible roles of this gene in PAH degradation in vivo. Interestingly, these mutant lines showed less accumulation of H 2 O 2 after PAH exposure. Transgenic lines over-expressing At5g05600 showed a hypersensitive response and more oxidative stress after phenanthrene treatments. Moreover, fluorescence spectra results of biochemical assays with the recombinant His-tagged protein AT5G05600 detected chemical modifications of phenanthrene. Taken together, these results support the hypothesis that AT5G05600 is involved in the catabolism of PAHs and the accumulation of toxic intermediates during PAH biotransformation in plants. This research represents the first step in the design of transgenic plants with the potential to degrade PAHs, leading to the development of vigorous plant varieties that can reduce the levels of these pollutants in the environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Ambient concentrations and personal exposure to polycyclic aromatic hydrocarbons (PAH) in an urban community with mixed sources of air pollution.

PubMed

Zhu, Xianlei; Fan, Zhihua Tina; Wu, Xiangmei; Jung, Kyung Hwa; Ohman-Strickland, Pamela; Bonanno, Linda J; Lioy, Paul J

2011-01-01

Assessment of the health risks resulting from exposure to ambient polycyclic aromatic hydrocarbons (PAH) is limited by a lack of environmental exposure data among the general population. This study characterized personal exposure and ambient concentrations of PAH in the Village of Waterfront South (WFS), an urban community with many mixed sources of air toxics in Camden, New Jersey, and CopeWood/Davis Streets (CDS), an urban reference area located ∼1 mile east of WFS. A total of 54 and 53 participants were recruited from non-smoking households in WFS and CDS, respectively. In all, 24-h personal and ambient air samples were collected simultaneously in both areas on weekdays and weekends during summer and winter. The ambient PAH concentrations in WFS were either significantly higher than or comparable to those in CDS, indicating the significant impact of local sources on PAH pollution in WFS. Analysis of diagnostic ratios and correlation suggested that diesel truck traffic, municipal waste combustion and industrial combustion were the major sources in WFS. In such an area, ambient air pollution contributed significantly to personal PAH exposure, explaining 44-96% of variability in personal concentrations. This study provides valuable data for examining the impact of local ambient PAH pollution on personal exposure and therefore potential health risks associated with environmental PAH pollution.

Ambient concentrations and personal exposure to polycyclic aromatic hydrocarbons (PAH) in an urban community with mixed sources of air pollution

PubMed Central

ZHU, XIANLEI; FAN, ZHIHUA (TINA); WU, XIANGMEI; JUNG, KYUNG HWA; OHMAN-STRICKLAND, PAMELA; BONANNO, LINDA J.; LIOY, PAUL J.

2014-01-01

Assessment of the health risks resulting from exposure to ambient polycyclic aromatic hydrocarbons (PAH) is limited by a lack of environmental exposure data among the general population. This study characterized personal exposure and ambient concentrations of PAH in the Village of Waterfront South (WFS), an urban community with many mixed sources of air toxics in Camden, New Jersey, and CopeWood/Davis Streets (CDS), an urban reference area located ~1 mile east of WFS. A total of 54 and 53 participants were recruited from non-smoking households in WFS and CDS, respectively. In all, 24-h personal and ambient air samples were collected simultaneously in both areas on weekdays and weekends during summer and winter. The ambient PAH concentrations in WFS were either significantly higher than or comparable to those in CDS, indicating the significant impact of local sources on PAH pollution in WFS. Analysis of diagnostic ratios and correlation suggested that diesel truck traffic, municipal waste combustion and industrial combustion were the major sources in WFS. In such an area, ambient air pollution contributed significantly to personal PAH exposure, explaining 44–96% of variability in personal concentrations. This study provides valuable data for examining the impact of local ambient PAH pollution on personal exposure and therefore potential health risks associated with environmental PAH pollution. PMID:21364704

Physical and chemical characterization of representative samples of recycled rubber from end-of-life tires.

PubMed

Re Depaolini, Andrea; Bianchi, Giancarlo; Fornai, Daniele; Cardelli, Angela; Badalassi, Marco; Cardelli, Camillo; Davoli, Enrico

2017-10-01

A large number of end-of-life tires (ELTs) were sampled and classified by type, age and origin to obtain recycled rubber samples representative of the materials placed on the Italian market. The selected recycled tire rubber samples were physically and chemically characterized and a chemometric approach was used to determine correlations. The polycyclic aromatic hydrocarbons (PAHs) content was correlated to the aromaticity index and a model was built to establish the H-Bay aromaticity index (H-Bay) from the PAH concentrations. ELT of different origin and age produced in non-European countries generally had higher PAH content and a higher H-Bay index. H-Bay values of all the samples were lower than the REACH limits and old tires had higher aromatic content than recent ones, possibly due to the replacement of aromatic oils in tire production. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Pulmonary Arterial Hypertension: A Focus on Infused Prostacyclins.

PubMed

Stewart, Traci

2016-01-01

Pulmonary arterial hypertension (PAH) is characterized by vasoconstriction and cell proliferation in the pulmonary vasculature. Guideline-driven interventions with infused prostacyclin treatment are the mainstay for patients with advanced symptoms. Infused prostacyclin therapy is complex. It is critical to manage prostacyclin therapy with precision because boluses or interruptions can be fatal. Education of patients and inpatient staff nurses is necessary to prevent negative outcomes. Nurses are an essential part of the multidisciplinary team caring for patients with PAH. The diagnostic evaluation and treatment of PAH are reviewed here, and challenges associated with the care of patients on prostacyclin therapy are discussed.

Phototoxicity of three PAHs to Chironomus tentans in the presence and absence of a metabolic inhibitor

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

Monson, P.D.; Sheedy, B.R.; Cox, J.S.

1995-12-31

Chironomus tentans has been observed to be insensitive to photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) relative to other benthic test species. The midge is generally accepted to have the ability to metabolize organic compounds (e.g. pesticides) via the cytochrome P450 monooxygenase system, which may explain in part the organisms insensitivity. The objective of this study was to characterize the enhanced effects, if any, of a metabolic inhibitor of P450, piperonyl butoxide (PBO) on the phototoxicity and tissue concentrations of three PAHs (fluoranthene, anthracene and pyrene) using C. tentans. Results indicated that phototoxicity (time to mortality) to the midge exposedmore » to PAH + PBO followed the order fluoranthene > pyrene {much_gt} anthracene. These differences in phototoxicity were not as marked in exposures without PBO. However, based on a lethal tissue dose (LD50), anthracene was the most toxic of the three. Tissue concentrations corresponded with toxicity results in that higher concentrations of PAH accumulated in exposures containing PBO. Though presence of PBO increased tissue concentrations and phototoxicity of the PAHs to the midge, the differences were slight and suggest that metabolism of PAHs by the cytochrome P450 pathway is not solely responsible for the midges relative insensitivity to this class of compounds.« less

Polycyclic Aromatic Hydrocarbons (PAHs) produced in the combustion of fatty acid alkyl esters from different feedstocks: Quantification, statistical analysis and mechanisms of formation.

PubMed

Llamas, Alberto; Al-Lal, Ana-María; García-Martínez, María-Jesús; Ortega, Marcelo F; Llamas, Juan F; Lapuerta, Magín; Canoira, Laureano

2017-05-15

Polycyclic Aromatic Hydrocarbons (PAHs) are pollutants of concern due to their carcinogenic and mutagenic activity. Their emissions are mainly related with the combustion or pyrolysis of the organic matter, such as in fossil fuels combustion. It is important to characterize PAHs in the combustions of biofuels due to their increasing importance in the actual energetic setting. There is a lot of research focused in PAHs emission due to the combustion in diesel engines; but only few of them have analyzed the effect of raw material and type of alcohol used in the transesterification process. Different raw materials (i.e. animal fat, palm, rapeseed, linseed, peanut, coconut, and soybean oils) have been used for obtaining FAME and FAEE. A method for measuring PAHs generated during combustion in a bomb calorimeter has been developed. Combustion was made at different oxygen pressures and the samples were taken from the bomb after each combustion. Samples were extracted and the PAHs amounts formed during combustion were analyzed by GC-MS. This research shows the statistical relationships among the 16 PAHs of concern, biodiesel composition and oxygen pressure during combustion. Copyright © 2017 Elsevier B.V. All rights reserved.

DNA Damage and Pulmonary Hypertension

PubMed Central

Ranchoux, Benoît; Meloche, Jolyane; Paulin, Roxane; Boucherat, Olivier; Provencher, Steeve; Bonnet, Sébastien

2016-01-01

Pulmonary hypertension (PH) is defined by a mean pulmonary arterial pressure over 25 mmHg at rest and is diagnosed by right heart catheterization. Among the different groups of PH, pulmonary arterial hypertension (PAH) is characterized by a progressive obstruction of distal pulmonary arteries, related to endothelial cell dysfunction and vascular cell proliferation, which leads to an increased pulmonary vascular resistance, right ventricular hypertrophy, and right heart failure. Although the primary trigger of PAH remains unknown, oxidative stress and inflammation have been shown to play a key role in the development and progression of vascular remodeling. These factors are known to increase DNA damage that might favor the emergence of the proliferative and apoptosis-resistant phenotype observed in PAH vascular cells. High levels of DNA damage were reported to occur in PAH lungs and remodeled arteries as well as in animal models of PH. Moreover, recent studies have demonstrated that impaired DNA-response mechanisms may lead to an increased mutagen sensitivity in PAH patients. Finally, PAH was linked with decreased breast cancer 1 protein (BRCA1) and DNA topoisomerase 2-binding protein 1 (TopBP1) expression, both involved in maintaining genome integrity. This review aims to provide an overview of recent evidence of DNA damage and DNA repair deficiency and their implication in PAH pathogenesis. PMID:27338373

Effects-driven chemical fractionation of heavy fuel oil to isolate compounds toxic to trout embryos.

PubMed

Bornstein, Jason M; Adams, Julie; Hollebone, Bruce; King, Thomas; Hodson, Peter V; Brown, R Stephen

2014-04-01

Heavy fuel oil (HFO) spills account for approximately 60% of ship-source oil spills and are up to 50 times more toxic than medium and light crude oils. Heavy fuel oils contain elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) and alkyl-PAHs, known to be toxic to fish; however, little direct characterization of HFO toxicity has been reported. An effects-driven chemical fractionation was conducted on HFO 7102 to separate compounds with similar chemical and physical properties, including toxicity, to isolate the groups of compounds most toxic to trout embryos. After each separation, toxicity tests directed the next phase of fractionation, and gas chromatography-mass spectrometry analysis correlated composition with toxicity, with a focus on PAHs. Low-temperature vacuum distillation permitted the separation of HFO into 3 fractions based on boiling point ranges. The most toxic of these fractions underwent wax precipitation to remove long-chain n-alkanes. The remaining PAH-rich extract was further separated using open column chromatography, which provided distinct fractions that were grouped according to increasing aromatic ring count. The most toxic of these fractions was richest in PAHs and alkyl-PAHs. The results of the present study were consistent with previous crude oil studies that identified PAH-rich fractions as the most toxic. © 2013 SETAC.

Evaluation of poly-aromatic hydrocarbons (PAHs) in the aquatic species of Suez Gulf water along El-Sokhna area to the Suez refineries.

PubMed

Ali, Nabila A; Ahmed, Omayma E; Doheim, Mamdouh M

2014-02-01

The Egyptian Red Sea environment especially along El-Sokhna area to the Suez refineries (Suez) is severely contaminated with organic compounds, as well as overfishing. This may be well contributory to recent serious declines in fish stocks. Fish embryos are also particularly vulnerable to oil exposure, even at extremely low concentrations of less than one part per billion. Consequently, even traces of oil pollution at levels often considered safe for wildlife can cause severe damage to fish. Sixteen polycyclic aromatic hydrocarbons (PAHs) were investigated in ten fish species of aquatic species by high performance liquid chromatography (HPLC). The compositions of PAHs determined in all samples were measured in order to use them as chemical markers for identifying different sources of PAH pollutants in the studied region. The total content of these16 PAHs ranged from 399.616 up to 67,631.779 ng/g wet weight. The data show that these values are considered to be alarmingly high enough to cause lethal toxicity effect by accumulation. All studied aquatic species samples are characterized by relatively high concentrations of the six-membered ring PAHs. The origin of PAHs in the collected samples is either petrogenic, biogenic, or mixed petrogenic and biogenic.

Transplacental transfer of polycyclic aromatic hydrocarbons in paired samples of maternal serum, umbilical cord serum, and placenta in Shanghai, China.

PubMed

Zhang, Xiaolan; Li, Xiaojing; Jing, Ye; Fang, Xiangming; Zhang, Xinyu; Lei, Bingli; Yu, Yingxin

2017-03-01

Prenatal exposure to polycyclic aromatic hydrocarbons (PAHs) is a high-priority public health concern. However, maternal to fetal transplacental transfer of PAHs has not been systematically studied. To investigate the transplacental transfer of PAHs from mother to fetus and determine the influence of lipophilicity (octanol-water partition coefficient, K OW ) on transfer process, in the present study, we measured the concentrations of 15 PAHs in 95 paired maternal and umbilical cord serum, and placenta samples (in total 285 samples) collected in Shanghai, China. The average concentration of total PAHs was the highest in maternal serums (1290 ng g -1 lipid), followed by umbilical cord serums (1150 ng g -1 lipid). The value was the lowest in placenta samples (673 ng g -1 lipid). Low molecular weight PAHs were the predominant compounds in the three matrices. Increases in fish and meat consumption did not lead to increases in maternal PAH levels, and no obvious gender differences in umbilical cord serums were observed. The widespread presence of PAHs in umbilical cord serums indicated the occurrence of transplacental transfer. The ratios of PAH concentrations in umbilical cord serum to those in maternal serum (F/M) and the concentrations in placenta to those in maternal serum (P/M) of paired samples were analyzed to characterize the transfer process of individual PAHs. Most F/M ratios on lipid basis were close to one (range: 0.79 to 1.36), which suggested that passive diffusion may control the transplacental transfer of PAHs from maternal serum to the fetal circulation. The P/M and F/M values calculated on lipid basis showed that PAHs with lower K OW were more likely to transfer from mother to fetus via the placenta. Copyright © 2016 Elsevier Ltd. All rights reserved.

Real-time measurements of jet aircraft engine exhaust.

PubMed

Rogers, Fred; Arnott, Pat; Zielinska, Barbara; Sagebiel, John; Kelly, Kerry E; Wagner, David; Lighty, JoAnn S; Sarofim, Adel F

2005-05-01

Particulate-phase exhaust properties from two different types of ground-based jet aircraft engines--high-thrust and turboshaft--were studied with real-time instruments on a portable pallet and additional time-integrated sampling devices. The real-time instruments successfully characterized rapidly changing particulate mass, light absorption, and polycyclic aromatic hydrocarbon (PAH) content. The integrated measurements included particulate-size distributions, PAH, and carbon concentrations for an entire test run (i.e., "run-integrated" measurements). In all cases, the particle-size distributions showed single modes peaking at 20-40nm diameter. Measurements of exhaust from high-thrust F404 engines showed relatively low-light absorption compared with exhaust from a turboshaft engine. Particulate-phase PAH measurements generally varied in phase with both net particulate mass and with light-absorbing particulate concentrations. Unexplained response behavior sometimes occurred with the real-time PAH analyzer, although on average the real-time and integrated PAH methods agreed within the same order of magnitude found in earlier investigations.

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.

Development of occlusive neointimal lesions in distal pulmonary arteries of endothelin B receptor-deficient rats: a new model of severe pulmonary arterial hypertension.

PubMed

Ivy, D Dunbar; McMurtry, Ivan F; Colvin, Kelley; Imamura, Masatoshi; Oka, Masahiko; Lee, Dong-Seok; Gebb, Sarah; Jones, Peter Lloyd

2005-06-07

Human pulmonary arterial hypertension (PAH) is characterized by proliferation of vascular smooth muscle and, in its more severe form, by the development of occlusive neointimal lesions. However, few animal models of pulmonary neointimal proliferation exist, thereby limiting a complete understanding of the pathobiology of PAH. Recent studies of the endothelin (ET) system demonstrate that deficiency of the ET(B) receptor predisposes adult rats to acute and chronic hypoxic PAH, yet these animals fail to develop neointimal lesions. Herein, we determined and thereafter showed that exposure of ET(B) receptor-deficient rats to the endothelial toxin monocrotaline (MCT) leads to the development of neointimal lesions that share hallmarks of human PAH. The pulmonary hemodynamic and morphometric effects of 60 mg/kg MCT in control (MCT(+/+)) and ET(B) receptor-deficient (MCT(sl/sl)) rats at 6 weeks of age were assessed. MCT(sl/sl) rats developed more severe PAH, characterized by elevated pulmonary artery pressure, diminished cardiac output, and right ventricular hypertrophy. In MCT(sl/sl) rats, morphometric evaluation revealed the presence of neointimal lesions within small distal pulmonary arteries, increased medial wall thickness, and decreased arterial-to-alveolar ratio. In keeping with this, barium angiography revealed diminished distal pulmonary vasculature of MCT(sl/sl) rat lungs. Cells within neointimal lesions expressed smooth muscle and endothelial cell markers. Moreover, cells within neointimal lesions exhibited increased levels of proliferation and were located in a tissue microenvironment enriched with vascular endothelial growth factor, tenascin-C, and activated matrix metalloproteinase-9, factors already implicated in human PAH. Finally, assessment of steady state mRNA showed that whereas expression of ET(B) receptors was decreased in MCT(sl/sl) rat lungs, ET(A) receptor expression increased. Deficiency of the ET(B) receptor markedly accelerates the progression of PAH in rats treated with MCT and enhances the appearance of cellular and molecular markers associated with the pathobiology of PAH. Collectively, these results suggest an overall antiproliferative effect of the ET(B) receptor in pulmonary vascular homeostasis.

Development of Occlusive Neointimal Lesions in Distal Pulmonary Arteries of Endothelin B Receptor–Deficient Rats: A New Model of Severe Pulmonary Arterial Hypertension

PubMed Central

Ivy, D. Dunbar; McMurtry, Ivan F.; Colvin, Kelley; Imamura, Masatoshi; Oka, Masahiko; Lee, Dong-Seok; Gebb, Sarah; Jones, Peter Lloyd

2007-01-01

Background Human pulmonary arterial hypertension (PAH) is characterized by proliferation of vascular smooth muscle and, in its more severe form, by the development of occlusive neointimal lesions. However, few animal models of pulmonary neointimal proliferation exist, thereby limiting a complete understanding of the pathobiology of PAH. Recent studies of the endothelin (ET) system demonstrate that deficiency of the ETB receptor predisposes adult rats to acute and chronic hypoxic PAH, yet these animals fail to develop neointimal lesions. Herein, we determined and thereafter showed that exposure of ETB receptor–deficient rats to the endothelial toxin monocrotaline (MCT) leads to the development of neointimal lesions that share hallmarks of human PAH. Methods and Results The pulmonary hemodynamic and morphometric effects of 60 mg/kg MCT in control (MCT+/+) and ETB receptor–deficient (MCTsl/sl) rats at 6 weeks of age were assessed. MCTsl/sl rats developed more severe PAH, characterized by elevated pulmonary artery pressure, diminished cardiac output, and right ventricular hypertrophy. In MCTsl/sl rats, morphometric evaluation revealed the presence of neointimal lesions within small distal pulmonary arteries, increased medial wall thickness, and decreased arterial-to-alveolar ratio. In keeping with this, barium angiography revealed diminished distal pulmonary vasculature of MCTsl/sl rat lungs. Cells within neointimal lesions expressed smooth muscle and endothelial cell markers. Moreover, cells within neointimal lesions exhibited increased levels of proliferation and were located in a tissue microenvironment enriched with vascular endothelial growth factor, tenascin-C, and activated matrix metalloproteinase-9, factors already implicated in human PAH. Finally, assessment of steady state mRNA showed that whereas expression of ETB receptors was decreased in MCTsl/sl rat lungs, ETA receptor expression increased. Conclusions Deficiency of the ETB receptor markedly accelerates the progression of PAH in rats treated with MCT and enhances the appearance of cellular and molecular markers associated with the pathobiology of PAH. Collectively, these results suggest an overall antiproliferative effect of the ETB receptor in pulmonary vascular homeostasis. PMID:15927975

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

Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in surface water from Liaohe River Basin, northeast China.

PubMed

Lv, Jiapei; Xu, Jian; Guo, Changsheng; Zhang, Yuan; Bai, Yangwei; Meng, Wei

2014-01-01

Liaohe River Basin is an important region in northeast China, which consists of several main rivers including Liao River, Taizi river, Daliao River, and Hun River. As a highly industrialized region, the basin receives dense waste discharges, causing severe environmental problems. In this study, the spatial and temporal distribution of aqueous polycyclic aromatic hydrocarbons (PAHs) in Liaohe River Basin from 50 sampling sites in both dry (May) and level (October) periods in 2012 was investigated. Sixteen USEPA priority PAHs were quantified by gas chromatography/mass selective detector. The total PAH concentration ranged from 111.8 to 2,931.6 ng/L in the dry period and from 94.8 to 2766.0 ng/L in the level period, respectively. As for the spatial distribution, the mean concentration of PAHs followed the order of Taizi River > Daliao River > Hun River > Liao River, showing higher concentrations close to large cities with dense industries. The composition and possible sources of PAHs in the water samples were also determined. The fractions of low molecular weight PAHs ranged from 58.2 to 93.3 %, indicating the influence of low or moderate temperature combustion process. Diagnostic ratios, principal component analysis, and hierarchical cluster analysis were used to study the possible source categories in the study area, and consistent results were obtained from different techniques, that PAHs in water samples mainly originated from complex sources, i.e., both pyrogenic and petrogenic sources. The benzo[a]pyrene equivalents (EBaP) characterizing the ecological risk of PAHs to the aquatic environment suggested that PAHs in Liaohe River Basin had already caused environmental health risks.

Solvent extracted organic matter and polycyclic aromatic hydrocarbons distributed in size-segregated airborne particles in a zone of México City: Seasonal behavior and human exposure

NASA Astrophysics Data System (ADS)

Amador-Muñoz, Omar; Villalobos-Pietrini, Rafael; Agapito-Nadales, Ma. Cristina; Munive-Colín, Zenaida; Hernández-Mena, Leonel; Sánchez-Sandoval, Magdalena; Gómez-Arroyo, Sandra; Bravo-Cabrera, José Luis; Guzmán-Rincón, Judith

2010-01-01

Airborne particulate mass was collected in a cascade impactor, and the mass concentration of solvent extracted organic matter (SEOM) and polycyclic aromatic hydrocarbons (PAH) were determined. A greater mass concentration of particles, SEOM and PAH were obtained in the dry season than in the rainy season for all impact stages; however, in the rainy season the proportion of SEOM/particles mass increased for all stages. There was an average decrease in particle mass concentration of 52.1 ± 6.7%, a 33.6 ± 12.3% decrease in SEOM and a 43.9 ± 16.9% decrease in heavy PAH (≥228 g mol -1) in the rainy season. Heavy PAH were distributed in fine particles, while light PAH were more abundant in coarse particles. Estimations of SEOM and PAH inhaled daily by a person were made. Considering the carcinogenic PAH median mass (10th-90th percentiles) in 20 m 3 of air, and the sum of all stages that could be inhaled daily by a person, estimates of 137 ng day -1 (74-246) in the dry season and 57 ng day -1 (21-101) in the rainy season were determined. The toxic equivalent factors were calculated to more accurately characterize the carcinogenic properties of PAH mixtures. This was based on the contribution of the carcinogenic potency of benzo[ a]pyrene. These estimations would need to be considered in establishing standards for Mexican air quality. Correlations were shown between other atmospheric pollutants and masses of particles, SEOM and PAH. Vehicles were suggested as an emission source for SEOM and PAH.

Characterization of elemental and polycyclic aromatic hydrocarbon compositions of urban air in Brisbane

NASA Astrophysics Data System (ADS)

Lim, McKenzie C. H.; Ayoko, Godwin A.; Morawska, Lidia

Characterization of the elemental and polycyclic aromatic hydrocarbons (PAHs) compositions of urban air was undertaken at three major sites in Brisbane, Australia. 17 elements and 16 US EPA priority PAHs were quantified at the sites. The most commonly detected elements in the TSP and PM 2.5 fractions were Al, Cd, Co, Cr, Cu, Fe, Mn, Mo, Si, Sn, Sr and Zn. Compared to the two other sites, PM 2.5 was found to contain higher concentrations of Zr, Mo, V, Al, Mn and Sr at the Queensland University of Technology (QUT) site. In contrast, the Woolloongabba sampling site, which was highly influenced by the vehicular emission and local industrial activities, has higher concentrations of Co, Sn, Cu, Zn and Mg while ANZ site has significantly lower concentration levels of most elements than the other sites; possibly due to the shielding effect of the nearby bush and forest. NAP, PHE, ANT, FLT, PYR and CRY were the most widespread PAHs found in all sites. But only QUT and Woolloongabba bus platform sites had detectable levels of the most carcinogenic US EPA PAH, BAP. The multi-criteria decision making procedures, Preference Ranking Organisation Method for Enrichment Evaluation (PROMETHEE) and Geometrical Analysis for Interactive Aid (GAIA) were used to rank the air samples and to identify the sources of the pollutants. Thus Woolloongabba bus platform was ranked as the most polluted site on the basis of the elemental and PAH compositions of its air samples while Woolloongabba bus platform and QUT sites were ranked as the worst polluted sites in terms of PAHs and PM 2.5 elemental contents, respectively.

A spatial approach to environmental risk assessment of PAH contamination.

PubMed

Bengtsson, Göran; Törneman, Niklas

2009-01-01

The extent of remediation of contaminated industrial sites depends on spatial heterogeneity of contaminant concentration and spatially explicit risk characterization. We used sequential Gaussian simulation (SGS) and indicator kriging (IK) to describe the spatial distribution of polycyclic aromatic hydrocarbons (PAHs), pH, electric conductivity, particle aggregate distribution, water holding capacity, and total organic carbon, and quantitative relations among them, in a creosote polluted soil in southern Sweden. The geostatistical analyses were combined with risk analyses, in which the total toxic equivalent concentration of the PAH mixture was calculated from the soil concentrations of individual PAHs and compared with ecotoxicological effect concentrations and regulatory threshold values in block sizes of 1.8 x 1.8 m. Most PAHs were spatially autocorrelated and appeared in several hot spots. The risk calculated by SGS was more confined to specific hot spot areas than the risk calculated by IK, and 40-50% of the site had PAH concentrations exceeding the threshold values with a probability of 80% and higher. The toxic equivalent concentration of the PAH mixture was dependent on the spatial distribution of organic carbon, showing the importance of assessing risk by a combination of measurements of PAH and organic carbon concentrations. Essentially, the same risk distribution pattern was maintained when Monte Carlo simulations were used for implementation of risk in larger (5 x 5 m), economically more feasible remediation blocks, but a smaller area became of great concern for remediation when the simulations included PAH partitioning to two separate sources, creosote and natural, of organic matter, rather than one general.

Importance of organic amendment characteristics on bioremediation of PAH-contaminated soil.

PubMed

Lukić, B; Huguenot, D; Panico, A; Fabbricino, M; van Hullebusch, E D; Esposito, G

2016-08-01

This study investigates the importance of the organic matter characteristics of several organic amendments (i.e., buffalo manure, food and kitchen waste, fruit and vegetables waste, and activated sewage sludge) and their influence in the bioremediation of a polycyclic aromatic hydrocarbons (PAH)-contaminated soil. The removal of low molecular weights (LMW) and high molecular weights (HMW) PAHs was monitored in four bioremediation reactors and used as an indicator of the role of organic amendments in contaminant removal. The total initial concentration of LMW PAHs was 234 mg kg(-1) soil (dry weight), while the amount for HMW PAHs was 422 mg kg(-1) soil (dry weight). Monitoring of operational parameters and chemical analysis was performed during 20 weeks. The concentrations of LMW PAH residues in soil were significantly lower in reactors that displayed a mesophilic phase, i.e., 11 and 15 %, compared to reactors that displayed a thermophilic phase, i.e., 29 and 31 %. Residual HMW PAHs were up to five times higher compared to residual LMW PAHs, depending on the reactor. This demonstrated that the amount of added organic matter and macronutrients such as nitrogen and phosphorus, the biochemical organic compound classes (mostly soluble fraction and proteins), and the operational temperature are important factors affecting the overall efficiency of bioremediation. On that basis, this study shows that characterization of biochemical families could contribute to a better understanding of the effects of organic amendments and clarify their different efficiency during a bioremediation process of PAH-contaminated soil.

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.

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.

Heavy metal-immobilizing organoclay facilitates polycyclic aromatic hydrocarbon biodegradation in mixed-contaminated soil.

PubMed

Biswas, Bhabananda; Sarkar, Binoy; Mandal, Asit; Naidu, Ravi

2015-11-15

Soils contaminated with a mixture of heavy metals and polycyclic aromatic hydrocarbons (PAHs) pose toxic metal stress to native PAH-degrading microorganisms. Adsorbents such as clay and modified clay minerals can bind the metal and reduce its toxicity to microorganisms. However, in a mixed-contaminated soil, an adsorption process more specific to the metals without affecting the bioavailability of PAHs is desired for effective degradation. Furthermore, the adsorbent should enhance the viability of PAH-degrading microorganisms. A metal-immobilizing organoclay (Arquad(®) 2HT-75-bentonite treated with palmitic acid) (MIOC) able to reduce metal (cadmium (Cd)) toxicity and enhance PAH (phenanthrene) biodegradation was developed and characterized in this study. The MIOC differed considerably from the parent clay in terms of its ability to reduce metal toxicity (MIOC>unmodified bentonite>Arquad-bentonite). The MIOC variably increased the microbial count (10-43%) as well as activities (respiration 3-44%; enzymatic activities up to 68%), and simultaneously maintained phenanthrene in bioavailable form in a Cd-phenanthrene mixed-contaminated soil over a 21-day incubation period. This study may lead to a new MIOC-assisted bioremediation technique for PAHs in mixed-contaminated soils. Copyright © 2015 Elsevier B.V. All rights reserved.

Enhanced adsorbability and photocatalytic activity of TiO2-graphene composite for polycyclic aromatic hydrocarbons removal in aqueous phase.

PubMed

Bai, Hongzhen; Zhou, Jun; Zhang, Hongjian; Tang, Guping

2017-02-01

Photodegradation via titanium dioxide (TiO 2 ) has been used to remove polycyclic aromatic hydrocarbons (PAHs) from environmental media broadly. In this study, a series of TiO 2 -graphene composites (P25-GR) with different GR weight ratios were synthesized via hydrothermal reaction of graphene oxide (GO) and P25. Their structures were characterized and the proprieties were tested in aqueous phase. Phenanthrene (PHE), fluoranthene (FLAN), and benzo[a]pyrene (BaP) were selected as models of PAHs. The experiment indicated that P25-2.5%GR exhibited enhancement in both adsorption and photodegradation, ∼80% of PAHs were removed after 2h photocatalysis. The influence of photodegradation rate was studied, including PAHs initial concentration and pH. Aromatic intermediates were identified during the reaction process and the degradation pathways were portrayed. This work explored the enhanced photocatalysis performance was attributed to the PAH-selective adsorbability and the strong electron transfer ability of the composite. The analysis of the degradation intermediates confirmed that the reaction proceeded with the formation of free radicals, leading to the gradual PAH mineralization. Copyright © 2016 Elsevier B.V. All rights reserved.

[Pulmonary arterial hypertension in women].

PubMed

Sanchez, O; Marié, E; Lerolle, U; Wermert, D; Israël-Biet, D; Meyer, G

2008-04-01

Pulmonary arterial hypertension (PAH) is a rare condition characterized by sustained elevation in pulmonary arterial resistance leading to right heart failure. PAH afflicts predominantly women. Echocardiography is the initial investigation of choice for non-invasive detection of PAH but right-heart catheterization is necessary to confirm the diagnosis. Conventional treatment includes non-specific drugs (warfarin, diuretics, oxygen). The endothelin-1 receptor antagonist bosentan, the phosphodiesterase-5 inhibitor sildenafil, and prostanoids have been shown to improve symptoms, exercise capacity and haemodynamics. Intravenous prostacyclin is the first-line treatment for the most severely affected patients. Despite the most modern treatment the overall mortality rate of pregnant women with severe PAH remains high. Therefore, pregnancy is contraindicated in women with PAH and an effective method of contraception is recommended in women of childbearing age. Therapeutic abortion should be offered, particularly when early deterioration occurs. If this option is not accepted, intravenous prostacyclin should be considered promptly. Recent advances in the management of PAH have markedly improved prognosis and have resulted in more women of childbearing age considering pregnancy. A multidisciplinary approach should give new insights into cardiopulmonary, obstetric and anaesthetic management during pregnancy, delivery and the post-partum period.

Biologically important compounds in synfuels processes

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

Clark, B R; Ho, C; Griest, W H

1980-01-01

Crude products, by-products and wastes from synfuel processes contain a broad spectrum of chemical compounds - many of which are active in biological systems. Discerning which compound classes are most important is necessary in order to establish effective control over release or exposure. Polycyclic aromatic hydrocarbons (PAH), multialkylated PAH, primary aromatic amines and N-heterocyclic PAH are significant contributors to the overall mutagenic activities of a large number of materials examined. Ames test data show that the basic, primary aromatic amine fraction is the most active. PAHs, multialkylated PAHs and N-heterocyclic PAHs are all components of the neutral fraction. In nearlymore » all cases, the neutral fractions contribute the largest portion of the mutagenic activity, while the basic primary aromatic amine fractions have the highest specific activity. Neutral fractions are usually the largest (wt %) whereas the total basic fractions are small by comparison; thus, the overall greater contribution of the neutral fraction to the mutagenic activity of most samples. Biologically active constituents are isolated in preparative scale amounts from complex mixtures utilizing combinations of liquid-liquid extraction and various liquid chromatographic column-eluant combinations. Fractions are characterized using a combination of spectroscopic techniques and gas chromatography/mass spectrometry.« less

Complex inheritance in Pulmonary Arterial Hypertension patients with several mutations

PubMed Central

Pousada, Guillermo; Baloira, Adolfo; Valverde, Diana

2016-01-01

Pulmonary Arterial Hypertension (PAH) is a rare and progressive disease with low incidence and prevalence, and elevated mortality. PAH is characterized by increased mean pulmonary artery pressure. The aim of this study was to analyse patients with combined mutations in BMPR2, ACVRL1, ENG and KCNA5 genes and to establish a genotype-phenotype correlation. Major genes were analysed by polymerase chain reaction (PCR) and direct sequencing. Genotype-phenotype correlation was performed. Fifty-seven (28 idiopathic PAH, 29 associated PAH group I) were included. Several mutations in different genes, classified as pathogenic by in silico analysis, were present in 26% of PAH patients. The most commonly involved gene was BMPR2 (12 patients) followed by ENG gene (9 patients). ACVRL1 and KCNA5 genes showed very low incidence of mutations (5 and 1 patients, respectively). Genotype-phenotype correlation showed statistically significant differences for gender (p = 0.045), age at diagnosis (p = 0.035), pulmonary vascular resistance (p = 0.030), cardiac index (p = 0.035) and absence of response to treatment (p = 0.011). PAH is consequence of a heterogeneous constellation of genetic arrangements. Patients with several pathogenic mutations seem to display a more severe phenotype. PMID:27630060

Occupational Exposure to Polycyclic Aromatic Hydrocarbon of Wildland Firefighters at Prescribed and Wildland Fires.

PubMed

Navarro, Kathleen M; Cisneros, Ricardo; Noth, Elizabeth M; Balmes, John R; Hammond, S Katharine

2017-06-06

Wildland firefighters suppressing wildland fires or conducting prescribed fires work long shifts during which they are exposed to high levels of wood smoke with no respiratory protection. Polycyclic aromatic hydrocarbons (PAHs) are hazardous air pollutants formed during incomplete combustion. Exposure to PAHs was measured for 21 wildland firefighters suppressing two wildland fires and 4 wildland firefighters conducting prescribed burns in California. Personal air samples were actively collected using XAD4-coated quartz fiber filters and XAD2 sorbent tubes. Samples were analyzed for 17 individual PAHs through extraction with dichloromethane and gas chromatograph-mass spectrometer analysis. Naphthalene, retene, and phenanthrene were consistently the highest measured PAHs. PAH concentrations were higher at wildland fires compared to prescribed fires and were highest for firefighters during job tasks that involve the most direct contact with smoke near an actively burning wildland fire. Although concentrations did not exceed current occupational exposure limits, wildland firefighters are exposed to PAHs not only on the fire line at wildland fires, but also while working prescribed burns and while off-duty. Characterization of occupational exposures from wildland firefighting is important to understand better any potential long-term health effects.

Distinct right ventricle remodeling in response to pressure overload in the rat.

PubMed

Mendes-Ferreira, P; Santos-Ribeiro, D; Adão, R; Maia-Rocha, C; Mendes-Ferreira, M; Sousa-Mendes, C; Leite-Moreira, A F; Brás-Silva, C

2016-07-01

Pulmonary arterial hypertension (PAH), the most serious chronic disorder of the pulmonary circulation, is characterized by pulmonary vasoconstriction and remodeling, resulting in increased afterload on the right ventricle (RV). In fact, RV function is the main determinant of prognosis in PAH. The most frequently used experimental models of PAH include monocrotaline- and chronic hypoxia-induced PAH, which primarily affect the pulmonary circulation. Alternatively, pulmonary artery banding (PAB) can be performed to achieve RV overload without affecting the pulmonary vasculature, allowing researchers to determine the RV-specific effects of their drugs/interventions. In this work, using two different degrees of pulmonary artery constriction, we characterize, in full detail, PAB-induced adaptive and maladaptive remodeling of the RV at 3 wk after PAB surgery. Our results show that application of a mild constriction resulted in adaptive hypertrophy of the RV, with preserved systolic and diastolic function, while application of a severe constriction resulted in maladaptive hypertrophy, with chamber dilation and systolic and diastolic dysfunction up to the isolated cardiomyocyte level. By applying two different degrees of constriction, we describe, for the first time, a reliable and short-duration PAB model in which RV adaptation can be distinguished at 3 wk after surgery. We characterize, in full detail, structural and functional changes of the RV in its response to moderate and severe constriction, allowing researchers to better study RV physiology and transition to dysfunction and failure, as well as to determine the effects of new therapies. Copyright © 2016 the American Physiological Society.

Control of Toxic Chemicals in Puget Sound, Phase 3: Study Of Atmospheric Deposition of Air Toxics to the Surface of Puget Sound

DTIC Science & Technology

2007-01-01

deposition directly to Puget Sound was an important source of PAHs, polybrominated diphenyl ethers (PBDEs), and heavy metals . In most cases, atmospheric...versus Atmospheric Fluxes ........................................................................66  PAH Source Apportionment ...temperature inversions) on air quality during the wet season. A semi-quantitative apportionment study permitted a first-order characterization of source

Urban air pollution and health risks of parent and nitrated polycyclic aromatic hydrocarbons in two megacities, southwest China

NASA Astrophysics Data System (ADS)

Zhuo, Shaojie; Du, Wei; Shen, Guofeng; Wang, Rui; Pan, Xuelian; Li, Tongchao; Han, Yang; Li, Yungui; Pan, Bo; Peng, Xing; Cheng, Hefa; Wang, Xilong; Shi, Guoliang; Xing, Baoshan; Tao, Shu

2017-10-01

Ambient air pollution in China has a significant spatial variation due to the uneven development and different energy structures. This study characterized ambient pollution of parent and nitrated polycyclic aromatic hydrocarbons (PAHs) through a 1-year measurement in two megacities in southwest China where regional PM2.5 levels were considerably lower than other regions. Though the annual average BaP levels in both two cities were below the national standard of 1.0 ng/m3, however, by taking other PAHs into account, PAHs pollution were serious as indicated by high BaP equivalent concentrations (BaPEQ) of 3.8 ± 2.6 and 4.4 ± 1.9 ng/m3, respectively. Risk assessment would be underestimated by nearly an order of magnitude if only using BaP in risk assessment compared to the estimation based on 26 PAHs including 16 priority and 10 non-priority isomers targeted in this study. Estimated incremental lifetime cancer risks (ILCR) were comparable at two cities, at about 330-380 persons per one million, even though the mass concentrations were significantly different. Nitrated PAHs showed distinct temporal and site differences compared to the parent PAHs. High cancer risks due to inhalation exposure of PAHs and their polar derivatives in the low PM2.5-pollution southwest China suggest essential and effective controls on ambient PAHs pollution in the region, and controls should take potential health risks into account instead of solely mass concentration.

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.

Effect of dibenzopyrene measurement on assessing air quality in Beijing air and possible implications for human health.

PubMed

Layshock, Julie; Simonich, Staci Massey; Anderson, Kim A

2010-12-01

Size fractionated particulate matter (PM) was collected in summer and winter from Beijing, China for the characterization of an expanded list of PAHs and evaluation of air pollution metrics. Summertime ΣPAHs on PM was 14.6 ± 29(PM 1.5), 0.88 ± 0.49(PM 1.5-7.2) and 0.29 ± 0.076(PM 7.2) ng m(-3) air while wintertime concentrations were 493 ± 206(PM 1.5), 26.7 ± 14(PM 1.5-7.2) and 5.3 ± 2.5(PM 7.2) ng m(-3) air. Greater than 90% of the carcinogenic PAHs were concentrated on PM(1.5). Dibenzopyrene isomers made up a significant portion (∼30%) of the total carcinogenic PAH load during the winter. To our knowledge, this is the first report of dibenzopyrenes in the Beijing atmosphere and among the few studies that report these highly potent PAHs in ambient particulate matter. Lifetime risk calculations indicated that 1 out of 10,000 to over 6 out of 100 Beijing residents may have an increased risk of lung cancer due to PAH concentration. Over half of the lifetime risk was attributed to Σdibenzopyrenes. The World Health Organization and Chinese daily PM(10) standard was exceeded on each day of the study, however, PAH limits were only exceeded during the winter. The outcomes of the air pollution metrics were highly dependent on the individual PAHs measured and seasonal variation.

Searching for Prebiotically Important Molecules in Protoplanetary Disks

NASA Astrophysics Data System (ADS)

Gibb, Erika L.; Brown, L. R.; Sudholt, E.

2012-05-01

Understanding how prebiotic molecules form and are distributed around young stars is an important step in determining how and where life can form in planetary systems. In general, protoplanetary disks consist of a cold, dense midplane where, beyond the frost line, water and organic molecules will condense onto dust grains as icy coatings. The surface of the disk is exposed to stellar and interstellar radiation, giving rise to a photon-dominated region characterized by ionization and dissociation products. Between these two layers is a warm molecular layer where a rich molecular chemistry is predicted to occur. The warm molecular layer is somewhat protected from ionizing radiation by the dust and polycyclic aromatic hydrocarbons (PAHs) in the surface region. We present a high-resolution (λ / Δλ 25,000), near-infrared spectroscopic survey of the L-band toward T Tauri star GV Tau N. The data were acquired with the NIRSPEC instrument on the Keck II telescope, located on Mauna Kea, HI. We detected strong HCN absorption lines that we interpret to be located in the warm molecular layer of a nearly edge-on protoplanetary disk. We discuss significant differences in spectra acquired in 2006 and 2010 and implications for the material in the disk of GV Tau N, including rotational temperatures, abundances, and inferred location. This work was supported by the NSF Stellar Astronomy Program (Grant #0908230) and the NASA Exobiology program (NNX11AG44G).

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification.

PubMed

Slezakova, K; Pires, J C M; Castro, D; Alvim-Ferraz, M C M; Delerue-Matos, C; Morais, S; Pereira, M C

2013-06-01

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM10 and PM2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO2, PM10, NO2, CO, and O3; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng m(-3), surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10(-6)) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98 × 10(-7) in PM10 and 1.06 × 10(-6) in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO2, NO2, PM10, CO, and solar radiation had positive correlation with PAHs concentrations, while O3, temperature, relative humidity, and wind speed were negatively correlated.

Novel Insight for Organic Matter Sourcing: Interest of Time Resolved Fluorescence to Qualify and Quantify PAH Content of Solid Matrix at High Resolution

NASA Astrophysics Data System (ADS)

Quiers, M.; Perrette, Y.; Jacq, K.; Pousset, E.; Plassart, G.

2017-12-01

OM fluorescence is today a well-developed tool used to characterize and quantify organic matter (OM), but also to evaluate and discriminate OM fate and changes related to climate and environmental modifications. While fluorescence measurements on water and soils extracts provide information about organic fluxes today, solid phase fluorescence using natural archives allows to obtain high resolution records of OM evolution during time. These evolutions can be discussed in regards of climate and environmental perturbations detected in archives using different proxies, and thus provide keys for understanding factors driving carbon fluxes mechanisms. Among fluorescent organic species, Polycyclic Aromatic Hydrocarbons (PAH) have been used as probe molecules for organic contamination tracking. Moreover, monitoring studies have shown that PAH could also be used as markers to discriminates atmospheric and erosion factors leading to PAH and organic matter fluxes to the aquifer. PAH records in soils and natural archives appear as a promising proxy to follow both past atmospheric contamination and soil erosion. But, PAH fluorescence is difficult to discriminate from bulk OM fluorescence using steady-state fluorescence (SSF) technics as their fluorescence domains recover. Time resolved emission spectroscopy (TRES) increases the information provided by SSF technic, adding a time dimension to measurements and allowing to discriminate PAH fluorescence. We report here a first application of this technic on natural archives. The challenge is to obtain TRES signature along the sample, including for low PAH concentrations. This study aims to evaluate the reliability of high resolution TRES measurement as PAH carbon fluxes sources. Method is based on LIF instrument for solid phase fluorescence measurement. An instrument coupling an excitation system constituting by 2 pulsed lasers (266 and 355 nm) and a detection system was developed. This measurement provides high resolution record of PAH fluorescence. Preliminary results on stalagmite samples, lake sediments and soils will be reported. PAH content variations along the sample were compared with PAH concentration and with bulk OM content deduced from SSF records. The accuracy of the PAH fluorescence as source marker of fluxes will be discussed for each type of sample.

Later life swimming performance and persistent heart damage following subteratogenic PAH mixture exposure in the Atlantic killifish (Fundulus heteroclitus).

PubMed

Brown, Daniel R; Thompson, Jasmine; Chernick, Melissa; Hinton, David E; Di Giulio, Richard T

2017-12-01

High-level, acute exposures to individual polycyclic aromatic hydrocarbons (PAHs) and complex PAH mixtures result in cardiac abnormalities in developing fish embryos. Whereas acute PAH exposures can be developmentally lethal, little is known about the later life consequences of early life, lower level PAH exposures in survivors. A population of PAH-adapted Fundulus heteroclitus from the PAH-contaminated Superfund site, Atlantic Wood Industries, Elizabeth River, Portsmouth, Virginia, United States, is highly resistant to acute PAH cardiac teratogenicity. We sought to determine and characterize long-term swimming performance and cardiac histological alterations of a subteratogenic PAH mixture exposure in both reference killifish and PAH-adapted Atlantic Wood killifish embryos. Killifish from a relatively uncontaminated reference site, King's Creek, Virginia, United States, and Atlantic Wood killifish were treated with dilutions of Elizabeth River sediment extract at 24 h post fertilization (hpf). Two proven subteratogenic dilutions, 0.1 and 1.0% Elizabeth River sediment extract (total PAH 5.04 and 50.4 µg/L, respectively), were used for embryo exposures. Then, at 5-mo post hatching, killifish were subjected to a swim performance test. A separate subset of these individuals was processed for cardiac histological analysis. Unexposed King's Creek killifish significantly outperformed the unexposed Atlantic Wood killifish in swimming performance as measured by Ucrit (i.e., critical swimming speed). However, King's Creek killifish exposed to Elizabeth River sediment extract (both 0.1 and 1.0%) showed significant declines in Ucrit. Histological analysis revealed the presence of blood in the pericardium of King's Creek killifish. Although Atlantic Wood killifish showed baseline performance deficits relative to King's Creek killifish, their pericardial cavities were nearly free of blood and atrial and ventricular alterations. These findings may explain, in part, the diminished swimming performance of King's Creek fish. Environ Toxicol Chem 2017;36:3246-3253. © 2017 SETAC. © 2017 SETAC.

The toxicity of creosote-treated wood to Pacific herring embryos and characterization of polycyclic aromatic hydrocarbons near creosoted pilings in Juneau, Alaska.

PubMed

Duncan, Danielle L; Carls, Mark G; Rice, Stanley D; Stekoll, Michael S

2017-05-01

Polycyclic aromatic hydrocarbons (PAHs) from creosote exposure in the laboratory resulted in deleterious effects in developing Pacific herring (Clupea pallasi) embryos, and potentially toxic concentrations of PAHs were measured using passive water samplers at 1 of 3 harbor field sites in Juneau, Alaska, USA. Aqueous total PAH concentrations of 4.6 μg/L and 8.4 μg/L from creosote exposure resulted in skeletal defects and ineffective swimming in hatched larvae in the laboratory (10% effective concentrations) and were the most sensitive parameters measured. Hatch rates also suffered from creosote exposure in a dose-dependent manner: at exposures between 5 μg/L and 50 μg/L total PAH, 50% of the population failed to hatch. Comparisons between laboratory and field deployed passive samplers suggested that for at least 1 harbor in Juneau, concentrations sufficient to induce teratogenic effects were found directly on creosoted pilings, within 10 cm of them, and sometimes at a distance of 10 m. Total PAH concentrations generally decreased with distance from creosoted pilings. Creosote pilings contribute to the PAH load within a marina and can rise to PAH concentrations that are harmful to fish embryos, but at a scale that is localized in the environment. Environ Toxicol Chem 2017;36:1261-1269. © 2016 SETAC. © 2016 SETAC.

Characterization of polycyclic aromatic hydrocarbons in fugitive PM10 emissions from an integrated iron and steel plant.

PubMed

Khaparde, V V; Bhanarkar, A D; Majumdar, Deepanjan; Rao, C V Chalapati

2016-08-15

Fugitive emissions of PM10 (particles <10μm in diameter) and associated polycyclic aromatic hydrocarbons (PAHs) were monitored in the vicinity of coking unit, sintering unit, blast furnace and steel manufacturing unit in an integrated iron and steel plant situated in India. Concentrations of PM10, PM10-bound total PAHs, benzo (a) pyrene, carcinogenic PAHs and combustion PAHs were found to be highest around the sintering unit. Concentrations of 3-ring and 4-ring PAHs were recorded to be highest in the coking unit whereas 5-and 6-ring PAHs were found to be highest in other units. The following indicatory PAHs were identified: indeno (1,2,3-cd) pyrene, dibenzo (a,h) anthracene, benzo (k) fluoranthene in blast furnace unit; indeno (1,2,3-cd) pyrene, dibenzo (a,h) anthracene, chrysene in sintering unit; Anthracene, fluoranthene, chrysene in coking unit and acenaphthene, fluoranthene, fluorene in steel making unit. Total-BaP-TEQ (Total BaP toxic equivalent quotient) and BaP-MEQ (Total BaP mutagenic equivalent quotient) concentration levels ranged from 2.4 to 231.7ng/m(3) and 1.9 to 175.8ng/m(3), respectively. BaP and DbA (dibenzo (a,h) anthracene) contribution to total-BaP-TEQ was found to be the highest. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Polycyclic Aromatic Hydrocarbon Sources and Trapping within Secondary Organic Aerosol

NASA Astrophysics Data System (ADS)

Wallace, H. W., IV; Sanchez, N. P.; Flynn, J. H., III; Lefer, B. L.; Bottenus, C. L. H.; VanReken, T. M.; Griffin, R. J.

2017-12-01

As part of the BEETEX field study, which occurred from Feburary 7 to 27, 2015, a mobile air quality laboratory was stationed near a major refinery proximate to the Houston Ship Channel to characterize the chemical nature and sources of atmospheric particulate matter (PM) using a high-resolution time-of-flight mass spectrometer. Positive matrix factorization (PMF) was performed on the organic signal of the aerosol mass spectra, resulting in five factors totaling an average of 4.1 μg/m3 of organic aerosol: hydrocarbon-like (0.67 μg/m3), cooking (0.35 μg/m3), biomass burning (1.14 μg/m3), low-volatility oxidized (1.15 μg/m3), and semi-volatile oxidized (0.78 μg/m3). As part of this study, two techniques to quantify particulate polycyclic aromatic hydrocarbons (PAHs) were compared: one capable of quantifying non-refractory molecular ion PAHs and the other sensitive only to surface bound PAHs. Together with PMF model results on the non-refractory organic PM data, we show that particulate PAHs likely are trapped inside secondary organic aerosol (SOA) as it deposits onto particles and that the two major sources of PAHs in the area are from biomass burning and use of internal combustion engines. Because this SOA may prevent particle-phase consumption of the PAH material, these results have important implications for long-range transport of particulate PAHs.

Identification and Quantification of Six-Ring C26H16 Cata-Condensed Polycyclic Aromatic Hydrocarbons in a Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar

PubMed Central

Oña-Ruales, Jorge O.; Sharma, Arun K.; Wise, Stephen A.

2015-01-01

We applied a combination of normal-phase liquid chromatography (NPLC) with ultraviolet-visible spectroscopy and gas chromatography with mass spectrometry (GC/MS) for the fractionation, identification, and quantification of six ring C26H16 cata-condensed polycyclic aromatic hydrocarbons, PAHs, in the Standard Reference Material 1597a, Complex Mixture of PAHs from Coal Tar. For the characterization analysis, we calculated the GC retention indices of 17 C26H16 PAH authentic reference standards using the Rxi-PAH and DB-5 GC columns. Then, we used NPLC with ultraviolet-visible spectroscopy to isolate the fractions containing the C26H16 PAHs, and subsequently, we used GC/MS to establish the identity and quantity of the C26H16 PAHs using authentic reference standards. Following this procedure, 12 C26H16 cata-condensed PAHs benzo[c]pentaphene, dibenzo[f,k]tetraphene, benzo[h]pentaphene, dibenzo[a,l]tetracene, dibenzo[c,k]tetraphene, naphtho[2,3-c]tetraphene, dibenzo[a,c]tetracene, benzo[b]picene, dibenzo[a,j]tetracene, naphtho[2,1-a]tetracene, dibenzo[c,p]chrysene, and dibenzo[a,f]tetraphene were identified and quantified for the first time, and benzo[c]picene was quantified for the first time in an environmental combustion sample. PMID:26449848

Preliminary Examination of the Interstellar Collector of Stardust

NASA Technical Reports Server (NTRS)

Westphal, A. J.; Allen, C.; Bastien, R.; Borg, J.; Brenker, F.; Bridges, J.; Brownlee, D. E.; Butterworth, A. L.; Floss, C.; Flynn, G.;

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.

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

Peroxidases from root exudates of Medicago sativa and Sorghum bicolor: Catalytic properties and involvement in PAH degradation.

PubMed

Dubrovskaya, Ekaterina; Pozdnyakova, Natalia; Golubev, Sergey; Muratova, Anna; Grinev, Vyacheslav; Bondarenkova, Anastasiya; Turkovskaya, Olga

2017-02-01

Peroxidases from root exudates of sorghum (Sorghum bicolor L. Moench) and alfalfa (Medicago sativa L.) were purified and characterized, and their ability to oxidize native PAHs and PAH-derivatives was evaluated. The obtained data confirm that peroxidases are involved in the rhizosphere degradation of PAHs. Nondenaturing PAGE showed that the peroxidases of both plants were represented by a range of isoforms/isoenzymes (five to eight). Minor forms were lost during further purification, and as a result, the major anionic form from alfalfa root exudates and the major cationic form from those of sorghum were obtained. Both electrophoretically homogeneous peroxidases were monomeric proteins with a molecular weight of about 46-48 kDa. The pH optima and the main catalytic constants for the test substrates were determined. On the basis of their molecular and catalytic properties, the obtained enzymes were found to be typical plant peroxidases. Derivatives of PAHs and potential products of their microbial degradation (9-phenanthrol and 9,10-phenanthrenequinone), unlike the parent PAH (phenanthrene), inhibited the catalytic activity of the peroxidases, possibly indicating greater availability of the enzymes' active centers to these substances. Peroxidase-catalyzed decreases in the concentrations of a number of PAHs and their derivatives were observed. Sorghum peroxidase oxidized anthracene and phenanthrene, while alfalfa peroxidase oxidized only phenanthrene. 1-Hydroxy-2-naphthoic acid was best oxidized by peroxidase of alfalfa. However, quinone derivatives of PAHs were unavailable to sorghum peroxidase, but were oxidized by alfalfa peroxidase. These results indicate that the major peroxidases from root exudates of alfalfa and sorghum can have a role in the rhizosphere degradation of PAHs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Novel therapeutic approaches for pulmonary arterial hypertension: Unique molecular targets to site-specific drug delivery.

PubMed

Vaidya, Bhuvaneshwar; Gupta, Vivek

2015-08-10

Pulmonary arterial hypertension (PAH) is a cardiopulmonary disorder characterized by increased blood pressure in the small arterioles supplying blood to lungs for oxygenation. Advances in understanding of molecular and cellular biology techniques have led to the findings that PAH is indeed a cascade of diseases exploiting multi-faceted complex pathophysiology, with cellular proliferation and vascular remodeling being the key pathogenic events along with several cellular pathways involved. While current therapies for PAH do provide for amelioration of disease symptoms and acute survival benefits, their full therapeutic potential is hindered by patient incompliance and off-target side effects. To overcome the issues related with current therapy and to devise a more selective therapy, various novel pathways are being investigated for PAH treatment. In addition, inability to deliver anti-PAH drugs to the disease site i.e., distal pulmonary arterioles has been one of the major challenges in achieving improved patient outcomes and improved therapeutic efficacy. Several novel carriers have been explored to increase the selectivity of currently approved anti-PAH drugs and to act as suitable carriers for the delivery of investigational drugs. In the present review, we have discussed potential of various novel molecular pathways/targets including RhoA/Rho kinase, tyrosine kinase, endothelial progenitor cells, vasoactive intestinal peptide, and miRNA in PAH therapeutics. We have also discussed various techniques for site-specific drug delivery of anti-PAH therapeutics so as to improve the efficacy of approved and investigational drugs. This review will provide gainful insights into current advances in PAH therapeutics with an emphasis on site-specific drug payload delivery. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of PAHs and metals in indoor/outdoor PM10/PM2.5/PM1 in a retirement home and a school dormitory.

PubMed

Hassanvand, Mohammad Sadegh; Naddafi, Kazem; Faridi, Sasan; Nabizadeh, Ramin; Sowlat, Mohammad Hossein; Momeniha, Fatemeh; Gholampour, Akbar; Arhami, Mohammad; Kashani, Homa; Zare, Ahad; Niazi, Sadegh; Rastkari, Noushin; Nazmara, Shahrokh; Ghani, Maryam; Yunesian, Masud

2015-09-15

In the present work, we investigated the characteristics of polycyclic aromatic hydrocarbons (PAHs) and metal(loid)s in indoor/outdoor PM10, PM2.5, and PM1 in a retirement home and a school dormitory in Tehran from May 2012 to May 2013. The results indicated that the annual levels of indoor and outdoor PM10 and PM2.5 were much higher than the guidelines issued by the World Health Organization (WHO). The most abundant detected metal(loid)s in PM were Si, Fe, Zn, Al, and Pb. We found higher percentages of metal(loid)s in smaller size fractions of PM. Additionally, the results showed that the total PAHs (ƩPAHs) bound to PM were predominantly (83-88%) found in PM2.5, which can penetrate deep into the alveolar regions of the lungs. In general, carcinogenic PAHs accounted for 40-47% of the total PAHs concentrations; furthermore, the smaller the particle size, the higher the percentage of carcinogenic PAHs. The percentages of trace metal(loid)s and carcinogenic PAHs in PM2.5 mass were almost twice as high as those in PM10. This can most likely be responsible for the fact that PM2.5 can cause more adverse health effects than PM10 can. The average BaP-equivalent carcinogenic (BaP-TEQ) levels both indoors and outdoors considerably exceeded the maximum permissible risk level of 1 ng/m(3) of BaP. The enrichment factors and diagnostic ratios indicated that combustion-related anthropogenic sources, such as gasoline- and diesel-fueled vehicles as well as natural gas combustion, were the major sources of PAHs and trace metal(loid)s bound to PM. Copyright © 2015 Elsevier B.V. All rights reserved.

Characteristics of polycyclic aromatic hydrocarbon (PAH) emissions from a UH-1H helicopter engine and its impact on the ambient environment

NASA Astrophysics Data System (ADS)

Chen, Yu-Cheng; Lee, Wen-Jhy; Uang, Shi-Nian; Lee, Su-Hsing; Tsai, Perng-Jy

The objective of this study is to characterize the emissions of polycyclic aromatic hydrocarbons (PAHs) from a UH-1H helicopter turboshaft engine and its impact on the ambient environment. Five power settings of the ground idle (GI), fly idle (FI), beed band check (BBC), inlet guide vane (IGV), and take off (TO) were selected and samples were collected from the exhaust by using an isokinetic sampling system. Twenty-two PAH compounds were analyzed by gas chromatograph (GC)/MS. We found the mean total PAH concentration in the exhaust of the UH-1H engine (843 μg m -3) is 1.05-51.7 times in magnitude higher than those of the heavy-duty diesel (HDD) engine, motor vehicle engine, and F101 aircraft engine. Two- and three-ringed PAHs account for 97.5% of total PAH emissions from the UH-1H engine. The mean total PAH and total BaP eq emission factors for the UH-1H engine (63.4 and 0.309 mg L -1·fuel) is 1.65-23.4 and 1.30-7.54 times in magnitude higher than those for the motor vehicle engine, HDD engine, and F101 aircraft engine. The total emission level of the single PAH compound, BaP, for the UH-1H engine (EL BaP) during one landing and take off (LTO) cycle (2.19 mg LTO -1) was higher than the European Commission standard (1.24 mg LTO -1) suggesting that appropriate measures should be taken to reduce PAH emissions from UH-1H engines in the future.

Urinary Concentrations of Polycyclic Aromatic Hydrocarbon Metabolites in Maté Drinkers in Rio Grande do Sul, Brazil

PubMed Central

Lopes, Antonio Barros; Metzdorf, Marcela; Metzdorf, Luiza; Ramalho, Marcos Paulo; Kavalco, Caroline; Etemadi, Arash; Pritchett, Natalie R.; Murphy, Gwen; Calafat, Antonia M.; Abnet, Christian C.; Dawsey, Sanford M.; Fagundes, Renato Borges

2017-01-01

Background Consumption of maté, an infusion of the herb Ilex paraguariensis (yerba maté), is associated with increased risk of esophageal squamous cell carcinoma (ESCC), but the carcinogenic mechanism is unclear. Commercial brands of yerba maté contain high levels of carcinogenic polycyclic aromatic hydrocarbons (PAHs), which are acquired during the traditional drying process. The purpose of this study was to characterize exposure to PAHs in maté drinkers over a wide range of maté consumption. Methods We recruited 244 adults who answered a questionnaire and collected a fasting spot urine specimen. We quantified urinary concentrations of seven PAH metabolites, and assessed associations between self-reported recent maté consumption and urinary PAH metabolites by multivariate regression. Results Recent maté consumption showed a significant dose-response association with 6 of 7 PAH metabolites in unadjusted models (p-for-trend <0.05). After adjustment for creatinine and potential confounders, concentrations of 2-naphthol, 1-hydroxyphenanthrene, and the sum of 2- and 3-hydroxyphenanthrene remained significantly associated with recent maté intake. The sum of the urinary concentrations of the phenanthrene metabolites was similar or higher among maté drinkers who did not smoke than among smokers who did not drink maté. Conclusions Urinary concentrations of PAH metabolites were significantly associated with self-reported amount of recent maté intake, and drinking maté increased urinary concentrations of some PAH metabolites as much as smoking cigarettes. Impact Drinking maté is a source of exposure to potentially carcinogenic PAHs, consistent with the hypothesis that the PAH content of maté may contribute to the increased risk of ESCC in maté drinkers. PMID:29263183

Urinary Concentrations of Polycyclic Aromatic Hydrocarbon Metabolites in Maté Drinkers in Rio Grande do Sul, Brazil.

PubMed

Lopes, Antonio Barros; Metzdorf, Marcela; Metzdorf, Luiza; Sousa, Marcos Paulo Ramalho; Kavalco, Caroline; Etemadi, Arash; Pritchett, Natalie R; Murphy, Gwen; Calafat, Antonia M; Abnet, Christian C; Dawsey, Sanford M; Fagundes, Renato Borges

2018-03-01

Background: Consumption of maté , an infusion of the herb Ilex paraguariensis (yerba maté) , is associated with increased risk of esophageal squamous cell carcinoma (ESCC), but the carcinogenic mechanism is unclear. Commercial brands of yerba maté contain high levels of carcinogenic polycyclic aromatic hydrocarbons (PAHs), which are acquired during the traditional drying process. The purpose of this study was to characterize exposure to PAHs in maté drinkers over a wide range of maté consumption. Methods: We recruited 244 adults who answered a questionnaire and collected a fasting spot urine specimen. We quantified urinary concentrations of seven PAH metabolites and assessed associations between self-reported recent maté consumption and urinary PAH metabolites by multivariate regression. Results: Recent maté consumption showed a significant dose-response association with 6 of 7 PAH metabolites in unadjusted models ( P trend < 0.05). After adjustment for creatinine and potential confounders, concentrations of 2-naphthol, 1-hydroxyphenanthrene, and the sum of 2- and 3-hydroxyphenanthrene remained significantly associated with recent maté intake. The sum of the urinary concentrations of the phenanthrene metabolites was similar or higher among maté drinkers who did not smoke than among smokers who did not drink maté Conclusions: Urinary concentrations of PAH metabolites were significantly associated with self-reported amounts of recent maté intake, and drinking maté increased urinary concentrations of some PAH metabolites as much as smoking cigarettes. Impact: Drinking maté is a source of exposure to potentially carcinogenic PAHs, consistent with the hypothesis that the PAH content of maté may contribute to the increased risk of ESCC in maté drinkers. Cancer Epidemiol Biomarkers Prev; 27(3); 331-7. ©2017 AACR . ©2017 American Association for Cancer Research.

Occurrence and particle-size distributions of polycyclic aromatic hydrocarbons in the ambient air of coking plant.

PubMed

Liu, Xiaofeng; Peng, Lin; Bai, Huiling; Mu, Ling; Song, Chongfang

2014-06-01

The purpose of this study was to characterize the occurrence and size distributions of ten species of polycyclic aromatic hydrocarbons (PAHs) in the ambient air of coking plants. Particulate-matter samples of four size fractions, including ≤2.1, 2.1-4.2, 4.2-10.2, and ≥10.2 μm, were collected using a Staplex234 cascade impactor during August 2009 at two coking plants in Shanxi, China. The PAHs were analyzed by a gas chromatograph equipped with a mass-selective detector. The concentrations of total particulate-matter PAHs were 1,412.7 and 2,241.1 ng/m(3) for plants I and II, and the distributions showed a peak within the 0.1-2.1 μm size range for plant I and the 0.1-4.2 μm for plant II. The size distributions of individual PAHs (except fluoranthene) exhibited a considerable peak within the 0.1-2.1 μm size range in coking plant I, which can be explained by the gas-particle partition mechanism. The ambient air of the coking plant was heavily polluted by PAHs associated with fine particles (≤2.1 μm), and benzo[b]fluoranthene made the largest contribution to total PAHs. The exposure levels of coking-plant workers to PAHs associated with fine particles were higher than to PAHs associated with coarse particles. Benzo[b]fluoranthene, benzo[a]pyrene, and dibenzo[a,h]anthracene should be the primary pollutants monitored in the coking plant. This research constitutes a significant contribution to assessing the exposure risk of coking-plant workers and providing basic data for PAH standards for ambient air in coking plants.

Developmental toxicity of PAH mixtures in fish early life stages. Part I: adverse effects in rainbow trout.

PubMed

Le Bihanic, Florane; Morin, Bénédicte; Cousin, Xavier; Le Menach, Karyn; Budzinski, Hélène; Cachot, Jérôme

2014-12-01

A new gravel-contact assay using rainbow trout, Oncorhynchus mykiss, embryos was developed to assess the toxicity of polycyclic aromatic hydrocarbons (PAHs) and other hydrophobic compounds. Environmentally realistic exposure conditions were mimicked with a direct exposure of eyed rainbow trout embryos incubated onto chemical-spiked gravels until hatching at 10 °C. Several endpoints were recorded including survival, hatching delay, hatching success, biometry, developmental abnormalities, and DNA damage (comet and micronucleus assays). This bioassay was firstly tested with two model PAHs, fluoranthene and benzo[a]pyrene. Then, the method was applied to compare the toxicity of three PAH complex mixtures characterized by different PAH compositions: a pyrolytic extract from a PAH-contaminated sediment (Seine estuary, France) and two petrogenic extracts from Arabian Light and Erika oils, at two environmental concentrations, 3 and 10 μg g(-1) sum of PAHs. The degree and spectrum of toxicity were different according to the extract considered. Acute effects including embryo mortality and decreased hatching success were observed only for Erika oil extract. Arabian Light and pyrolytic extracts induced mainly sublethal effects including reduced larvae size and hemorrhages. Arabian Light and Erika extracts both induced repairable DNA damage as revealed by the comet assay versus the micronucleus assay. The concentration and proportion of methylphenanthrenes and methylanthracenes appeared to drive the toxicity of the three PAH fractions tested, featuring a toxic gradient as follows: pyrolytic < Arabian Light < Erika. The minimal concentration causing developmental defects was as low as 0.7 μg g(-1) sum of PAHs, indicating the high sensitivity of the assay and validating its use for toxicity assessment of particle-bound pollutants.

Availability of polycyclic aromatic hydrocarbons from lampblack-impacted soils at former oil-gas plant sites in California, USA.

PubMed

Hong, Lei; Luthy, Richard G

2007-03-01

Lampblack-impacted soils at former oil-gas plant sites in California, USA, were characterized to assess the sorption of polycyclic aromatic hydrocarbons (PAHs) and the concentration-dependent effects of a residual oil tar phase on sorption mechanism and availability of PAHs. Nuclear magnetic resonance spectroscopy demonstrated similar aromaticity for both lampblack carbon and the oil tar phase, with pronounced resonance signals in the range of 100 to 150 ppm. Scanning-electron microscopic images revealed a physically distinct oil tar phase, especially at high concentrations in lampblack, which resulted in an organic-like film structure when lampblack particles became saturated with the oil tar. Sorption experiments were conducted on a series of laboratory-prepared lampblack samples to systematically evaluate influences of an oil tar phase on PAH sorption to lampblack. Results indicate that the sorption of PAHs to lampblack exhibits a competition among sorption phases at low oil tar contents when micro- and mesopores are accessible. When the oil tar content increases to more than 5 to 10% by weight, this tar phase fills small pores, reduces surface area, and dominates PAH sorption on lampblack surface. A new PAH partitioning model, Kd = KLB-C(1 - ftar)alpha + ftarKtar (alpha = empirical exponent), incorporates these effects in which the control of PAH partitioning transits from being dominated by sorption in lampblack (KLB-C) to absorption in oil tar (Ktar), depending on the fraction of tar (ftar). This study illustrates the importance of understanding interactions among PAHs, oil tar, and lampblack for explaining the differences in availability of PAHs among site soils and, consequently, for refining site-specific risk assessment and establishing soil cleanup levels.

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: environmental legacy after twelve years of the Gulf war oil spill.

PubMed

Bejarano, Adriana C; Michel, Jacqueline

2010-05-01

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU(FCV,43)). Samples were assigned to risk categories according to ESBTU(FCV,43) values: no-risk (< or = 1), low (>1 - < or = 2), low-medium (>2 - < or = 3), medium (>3 - < or = 5) and high-risk (>5). Sixty seven percent of samples had ESBTU(FCV,43) > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30 - <60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War. Copyright 2009 Elsevier Ltd. All rights reserved.

Lessons for Interstellar Travel from the Guidance and Control Design of the Near Earth Asteroid Scout Solar Sail Mission

NASA Technical Reports Server (NTRS)

Diedrich, Benjamin; Heaton, Andrew

2017-01-01

NASA's Near Earth Asteroid Scout (NEA Scout) solar sail mission will fly by and image an asteroid. The team has experience characterizing the sail forces and torques used in guidance, navigation, and control to meet the scientific objectives. Interstellar and precursor sail missions similarly require understanding of beam riding dynamics to follow sufficiently accurate trajectories to perform their missions. Objective: Identify the driving factors required to implement a guidance and control system that meets mission requirements for a solar sail mission; Compare experience of an asteroid flyby mission to interstellar missions to flyby and observe other stars or precursor missions to study the extrasolar medium.

Characterization of polycyclic aromatic hydrocarbons and carbonyl compounds in diesel exhaust emissions.

PubMed

Mabilia, Rosanna; Cecinato, Angelo; Tomasi Scianò, Maria Concetta; Di Palo, Vincenzo; Possanzini, Massimiliano

2004-01-01

Exhaust emissions from a recent model heavy-duty diesel vehicle (city bus) in a chassis dynamometer were measured during a transient driving cycle. Particle-bound polycyclic aromatic hydrocarbons (PAHs) and gaseous carbonyls, substances that create health hazards and are, as yet, unregulated were collected, the former on filters and the latter on dinitrophenylhydrazine (DNPH)-coated silica cartridges and analysed by GC-MS and HPLC, respectively. PAH emission rates decreased with the number of benzene fused rings. They averaged 0.2 mg km(-1) for a total of 11 PAHs ranging from fluoranthene to benzo(ghi)perylene. Fluoranthene and pyrene accounted for 90% of total PAHs. The sum of emission rates of C1 approximately C6 carbonyls averaged 174 mg km(-1), even if formaldehyde alone represented approximately 70% of the total carbonyl mass, followed by acetaldehyde (13%). Results obtained were compared with emission data reported in previous studies.

Characterization and source apportionment of polycyclic aromatic hydrocarbons (pahs) in the sediments of gulf of Pozzuoli (Campania, Italy).

PubMed

Arienzo, Michele; Donadio, Carlo; Mangoni, Olga; Bolinesi, Francesco; Stanislao, Corrado; Trifuoggi, Marco; Toscanesi, Maria; Di Natale, Gabriella; Ferrara, Luciano

2017-11-15

Most of the literature reports on the impact of the former Bagnoli brownfield on the pollution of Bagnoli Bay, embedded in the Gulf of Pozzuoli (GoP). Thus, we studied concentrations, types and sources of sixteen PAHs (EPA) in sediments at 22 sites along 5 transects covering the entire area of GoP. Outstanding levels of PAHs were found, varying from 7.1μgg -1 to 2.5 E+3μgg -1 . Sediments collected at sites far away from Bagnoli were found to be polluted to a similar extent than those facing the brownfield site, with values>100μgg -1 . Total PAHs levels in the sediments of GoP were higher by thirty-eleven thousand fold than those reported by other studies from various marine sites in the world. Transit axes of fine and very fine sands and diagnostic indexes revealed a common pyrolytic PAHs pollution spreading from the Bagnoli plant to all GoP. Copyright © 2017 Elsevier Ltd. All rights reserved.

A passive air sampler for characterizing the vertical concentration profile of gaseous phase polycyclic aromatic hydrocarbons in near soil surface air.

PubMed

Zhang, Yuzhong; Deng, Shuxing; Liu, Yanan; Shen, Guofeng; Li, Xiqing; Cao, Jun; Wang, Xilong; Reid, Brian; Tao, Shu

2011-03-01

Air-soil exchange is an important process governing the fate of polycyclic aromatic hydrocarbons (PAHs). A novel passive air sampler was designed and tested for measuring the vertical concentration profile of 4 low molecular weight PAHs in gaseous phase (PAH(LMW4)) in near soil surface air. Air at various heights from 5 to 520 mm above the ground was sampled by polyurethane foam disks held in down-faced cartridges. The samplers were tested at three sites: A: an extremely contaminated site, B: a site near A, and C: a background site on a university campus. Vertical concentration gradients were revealed for PAH(LMW4) within a thin layer close to soil surface at the three sites. PAH concentrations either decreased (Site A) or increased (Sites B and C) with height, suggesting either deposition to or evaporation from soils. The sampler is a useful tool for investigating air-soil exchange of gaseous phase semi-volatile organic chemicals. Copyright © 2010 Elsevier Ltd. All rights reserved.

Bioremoval of priority polycyclic aromatic hydrocarbons by a microbial community with high sorption ability.

PubMed

Sanches, Sandra; Martins, Mónica; Silva, Ana F; Galinha, Claudia F; Santos, Maria A; Pereira, Inês A C; Crespo, Maria Teresa Barreto

2017-02-01

The treatment of large volumes of wastewater during oil refining is presently a challenge. Bioremediation has been considered an eco-friendly approach for the removal of polycyclic aromatic hydrocarbons (PAHs), which are one of the most hazardous groups of organic micropollutants. However, it is crucial to identify native PAH-removing microorganisms for the development of an effective bioremediation process. This study reports the high potential of an anaerobic microbial consortium enriched from a petrochemical refinery wastewater to remove two priority PAHs-acenaphthene and phenanthrene. Seventy-seven percent of acenaphthene was removed within 17 h, whereas phenanthrene was no longer detected after 15 h. Bioremoval rates were extremely high (0.086 and 0.156 h -1 for acenaphthene and phenanthrene, respectively). The characterization of the microbial communities by next-generation sequencing and fluorescence in situ hybridization showed that the PAH-removing consortium was mainly composed by bacteria affiliated to Diaphorobacter and Paracoccus genera, independently of the PAH tested. Moreover, besides biodegradation, biosorption was a relevant mechanism involved in the removal of both PAHs, which is an important finding since biosorption is less expensive than biodegradation and can be carried out with dead biomass. Although biodegradation is the most commonly reported biological mechanism for PAH removal, this study demonstrated that biosorption by this microbial community may be extremely efficient for their removal. Given the outstanding ability of this microbial consortium to quickly remove the compounds addressed, it could be further applied for the bioremediation of PAHs in refinery wastewaters and other contaminated environments.

Pathophysiology of infantile pulmonary arterial hypertension induced by monocrotaline.

PubMed

Dias-Neto, Marina; Luísa-Neves, Ana; Pinho, Sónia; Gonçalves, Nádia; Mendes, Maria; Eloy, Catarina; Lopes, José M; Gonçalves, Daniel; Ferreira-Pinto, Manuel; Leite-Moreira, Adelino F; Henriques-Coelho, Tiago

2015-06-01

Pediatric pulmonary arterial hypertension (PAH) presents certain specific features. In this specific age group, experimental models to study the pathophysiology of PAH are lacking. To characterize hemodynamic, morphometric, and histological progression as well as the expression of neurohumoral factors and regulators of cardiac transcription in an infantile model of PAH induced by monocrotaline (MCT), eight-day-old Wistar rats were randomly injected with MCT (30 mg/kg, sc, n = 95) or equal volume of saline solution (n = 92). Animals were instrumented for biventricular hemodynamic recording 7, 14, and 21 days after MCT, whereas samples were collected at 1, 3, 7, 14, and 21 days after MCT. Different time point postinjections were defined for further analysis. Hearts and lungs were collected for morphometric characterization, assessment of right- and left-ventricle (RV and LV) cardiomyocyte diameter and collagen type-I and type-III ratio, RV collagen volume fraction, and pulmonary vessels wall thickness. mRNA quantification was undertaken for brain natriuretic peptide (BNP), endothelin-1 (ET-1), and for cardiac transcription regulators (HOP and Islet1). Animals treated with MCT at the 8th day of life presented RV hypertrophy since day 14 after MCT injection. There were no differences on the RV collagen volume fraction or collagen type-I and type-III ratio. Pulmonary vascular remodelling and PAH were present on day 21, which were accompanied by an increased expression of BNP, ET-1, HOP, and Islet1. The infantile model of MCT-induced PAH can be useful for the study of its pathophysiology and to test new therapeutic targets in pediatric age group.

Characterization of particulate-bound PAHs in rural households using different types of domestic energy in Henan Province, China.

PubMed

Wu, Fuyong; Liu, Xueping; Wang, Wei; Man, Yu Bon; Chan, Chuen Yu; Liu, Wenxin; Tao, Shu; Wong, Ming Hung

2015-12-01

The concentrations and composition of sixteen PAHs adsorbed to respirable particulate matter (PM10≤10 μm) and inhalable particulate matter (PM2.5≤2.5 μm) were determined during autumn and winter in rural households of Henan Province, China, which used four types of domestic energy [crop residues, coal, liquid petroleum gas (LPG) and electricity] for cooking and heating. The present results show that there were significantly (p<0.05) seasonal variations of particulate-bound PAHs in the rural households. The daily mean concentrations of particulate-bound PAHs in the kitchens, sitting rooms and outdoors were apparently higher in winter than those in autumn, except those in the kitchens using coal. The present study also shows that there were obvious variations of particulate-bound PAHs among the four types of domestic energy used in the rural households. The households using LPG for cooking can, at least in some circumstances, have higher concentrations of PAHs in the kitchens than using crop residues or electricity. In addition, using coal in the sitting rooms seemed to result in apparently higher concentrations of particulate-bound PAHs than using the other three types of domestic energy during winter. The most severe contamination occurred in the kitchens using LPG in winter, where the daily mean concentrations of PM2.5-bound PAHs were up to 762.5±931.2 ng m(-3), indicating that there was serious health risk of inhalation exposure to PAHs in the rural households of Henan Province. Rural residents' exposure to PM2.5-bound PAHs in kitchens would be roughly reduced by 69.8% and 85.5% via replacing coal or crop residues with electricity in autumn. The pilot research would provide important supplementary information to the indoor air pollution studies in rural area. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Concentrations and bioaccessibility of polycyclic aromatic hydrocarbons in wastewater-irrigated soil using in vitro gastrointestinal test.

PubMed

Khan, Sardar; Cao, Qing; Lin, Ai-Jun; Zhu, Yong-Guan

2008-06-01

Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of soil environment. Soil ingestion is of increasing concern for assessing health risk from PAH-contaminated soils because soil ingestion is one of the potentially important pathways of exposure to environmental pollutants, particularly relevant for children playing at contaminated sites due to their hand-to-mouth activities. In vitro gastro-intestinal tests imitate the human digestive tract, based on the physiology of humans, generally more simple, less time-consuming, and especially more reproducible than animal tests. This study was conducted to investigate the level of PAH contamination and oral bioaccessibility in surface soils, using physiologically based in vitro gastro-intestinal tests regarding both gastric and small intestinal conditions. Wastewater-irrigated soils were sampled from the metropolitan areas of Beijing and Tianjin, China, which were highly contaminated with PAHs. Reference soil samples were also collected for comparisons. At each site, four soils were sampled in the upper horizon at the depth of 0-20 cm randomly and were bulked together to form one composite sample. PAH concentrations and origin were investigated and a physiologically based in vitro test was conducted using all analytical grade reagents. Linear regression model was used to assess the relationship between total PAH concentrations in soils and soil organic carbon (SOC). A wide range of total PAH concentrations ranging from 1,304 to 3,369 mug kg(-1) in soils collected from different wastewater-irrigated sites in Tianjin, while ranging from 2,687 to 4,916 mug kg(-1) in soils collected from different wastewater-irrigated sites in Beijing, was detected. In general, total PAH concentrations in soils from Beijing sites were significantly higher than those from Tianjin sites, indicating a dominant contribution from both pyrogenic and petrogenic sources. Results indicated that the oral bioaccessibility of PAHs in small intestinal was significantly higher (from P < 0.05 to P < 0.001) than gastric condition. Similarly, the oral bioaccessibility of PAHs in contaminated sites was significantly higher (from P < or = 0.05 to P < 0.001) than in reference sites. Individual PAH ratios (three to six rings), a more accurate and reliable estimation about the emission sources, were used to distinguish the natural and anthropogenic PAH inputs in the soils. Results indicated that PAHs were both pyrogenic and petrogenic in nature. The identification of PAH sources and importance of in vitro test for PAH bioaccessibility were emphasized in this study. The oral bioaccessibility of individual PAHs in soils generally decreased with increasing ring numbers of PAHs in both the gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric conditions to that in the small intestinal condition generally increased with increasing ring numbers, indicating the relatively pronounced effect of bile extract on improving the bioaccessibility of PAHs with relatively high ring numbers characterized by their high K ( ow ) values. Similarly, total PAH concentrations in soils were strongly correlated with SOC, indicating that SOC was the key factor determining the retention of PAHs in soils. Soils were contaminated with PAHs due to long-term wastewater irrigation. PAHs with two to six rings showed high concentrations with a significant increase over reference soils. Based on the molecular indices, it was suggested that PAHs in soils had both pyrogenic and petrogenic sources. It was also concluded that the oral bioaccessibility of total PAHs in the small intestinal condition was significantly higher than that in the gastric condition. Furthermore, the bioaccessibility of individual PAHs in soils generally decreased with the increasing ring numbers in both the gastric and small intestinal conditions. It is suggested that more care should be given while establishing reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-to-mouth activities.

An Emission Inventory of Polycyclic Aromatic Hydrocarbons in China

NASA Astrophysics Data System (ADS)

Mu, Xilong; Zhu, Xianlei; Wang, Xuesong

2015-04-01

Polycyclic Aromatic Hydrocarbons (PAHs) are among the most dangerous compounds due to their high carcinogenic and mutagenic character. Emission inventory provides the primary data to account for the sources of ambient PAHs and server as a necessary database for effective PAHs pollution control. China is experiencing fast economic growth and large energy consumption, which might result in a large amount of PAHs anthropogenic emissions. Therefore, based on the previous studies and combined recently field emission measurements as well as socio-economic activity data, the development of a nationwide PAHs emission inventory is needed. In this work, the emission inventory of 16 PAHs listed as U.S. Environmental Protection Agency priority pollutants in China in the year 2012 is compiled. The emission amounts of PAHs were estimated as annual rates of emission-related activities multiplied by respective emission factors. The activities such as fuel consumption, including fossil fuel and biofuel, and socio-economic statistics were obtained from yearbook released by Chinese central government and/or provincial governments, as well as related industry reports. Emission factors were derived from the related literature. Recently reported emission factors from local measurements were used. The total emissions of PAHs were 120611 ton in 2012. In China, PAHs were emitted predominantly from domestic combustion of coal and biofuel, coking industry and motor vehicles, accounting for 72% of the total amount. PAHs emission profiles were significantly different between China and the other countries. The emission profile in China featured a relatively higher portion of high molecular weight species with carcinogenic potential due to large contributions of domestic combustion and coking industry. Domestic combustion of straw, coal and firewood emitted 19464 ton, 8831 ton, and 5062 ton of PAHs, respectively, which were much higher than those in other countries. Emission per capita showed geographical variations. In general, the southeastern provinces of China were characterized by higher emission per capita. The PAHs emissions were higher in the winter than those in the summer. In the following work, the above emission inventory will be used as an input to Chemical Transport Model to simulate the ambient PAHs concentrations in China, and the uncertainty of the inventory will be assessed based on the comparisons between simulated concentrations and available observations. Acknowledgement This work was financially supported by the Natural Science Foundation of China (Grant No. 41175102). Corresponding author: Xuesong Wang

Relationship of pyrogenic polycyclic aromatic hydrocarbons contamination among environmental solid media.

PubMed

Kim, Dong Won; Kim, Seung Kyu; Lee, Dong Soo

2009-06-01

This study compared the contamination levels and compositional characteristics of PAHs in soil, SS and sediment to understand the cross media characteristics among the three solid media and ecological risk implications for the purpose to help manage in a more integrated manner the environmental quality objectives or the ecological risk in the media. The study area included urban (metropolis and industrial zone), suburban and rural sites. Seasonal samples were concurrently collected in surface soils, surface waters (dissolved and suspended solid (SS) phases separately) and sediments. The emission estimate and source characterizing PAH indices consistently indicated that PAHs were from pyrogenic sources. The level of total PAHs in soil declined along the wind direction from the urban areas to the rural areas. The sorption power of soil appeared distinctly different between the urban and rural areas. The contamination levels and PAH profiles in soil and sediment were closely related to each other while no such correlation was observed between SS and sediment or SS and soil. Comparisons of the observed partitioning coefficients with three different partitioning equilibrium models strongly suggested that PAHs in water appeared to undergo partitioning among the dissolved phase in water, dissolved organic matter, and organic and soot carbons in SS, which might account for the level and profile of PAHs in SS that were not correlated with those in soil or sediment. The observed results suggested that PAHs of pyrogenic origins entered into soil, sediment, and water by the atmospheric deposition and subsequent other cross-media transfers of PAHs. The results also evidenced that sediments were principally contaminated with PAHs delivered via surface run-off from soil although in the urban areas the run-off influence appeared less immediate than in the rural areas. Environmental quality objectives for PAHs in soil and sediment should be set in a coherent manner and the protection efforts for the sediment quality should be made with the consideration of the soil quality particularly where the river bottom sediment is renewed periodically with eroded soil due to heavy rain and/or large river regime coefficient. In spite of the difference in PAH profiles among the three solid media, BaP commonly appeared to present the greatest TEQ, suggesting that strict regulation of BaP is necessary to efficiently and substantially minimize the total risk of the environmental PAHs.

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.

Identification of acute toxicants in New Bedford Harbor sediments

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

Ho, K.T.; McKinney, R.A.; Kuhn, A.

1997-03-01

New Bedford Harbor (NBH) is a marine Superfund site contaminated with high concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and metals. Experiments were conducted to determine the causal toxic agent(s) in pore waters from New Bedford Harbor sediments to amphipods and mysid shrimp. Chemical manipulations to characterize toxicity revealed that pore-water toxicity was organic in nature. Fractionation and subsequent mass spectral identification of peaks in the toxic fraction indicated that PCBs. PAHs, and unknown compounds were present. Comparisons of PAH LC50s and PAH concentrations in this fraction indicated that the toxicity was not due to PAHs because themore » PAH concentrations were much lower than the reported PAH LC50s. One unknown peak was positively identified as bis(2-ethylhexyl) phthalate, and the other tentatively identified as pyrazole. Toxicity tests and comparison of toxicity in the blank and toxic fractions eliminated the two unknowns as toxic causal agents. The authors determined the range of PCB LC50s to fall between 10 and 110 ppb for Mysidopsis bahia and Ampelisca abdita. Concentrations of PCBs for the toxic fractions ranged from 12 to 27 ppb. This range falls within the observed PCB LC50s for M. bahia and A. abdita. Based upon these PCB concentrations, they concluded that PCBs were the acute toxic agents in NBH pore waters. Other compounds in the toxic fractions, or compounds that coeluted and were undistinguished from PCBs had minor contributions to the measured toxicity.« less

Final Reports of the Stardust ISPE: Seven Probable Interstellar Dust Particles

NASA Technical Reports Server (NTRS)

Allen, Carlton; Sans Tresseras, Juan-Angel; Westphal, Andrew J.; Stroud, Rhonda M.; Bechtel, Hans A.; Brenker, Frank E.; Butterworth, Anna L.; Flynn, George J.; Frank, David R.; Gainsforth, Zack;

[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.

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.

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.

Spectroscopy and thermal modelling of the first interstellar object 1I/2017 U1 `Oumuamua

NASA Astrophysics Data System (ADS)

Fitzsimmons, Alan; Snodgrass, Colin; Rozitis, Ben; Yang, Bin; Hyland, Méabh; Seccull, Tom; Bannister, Michele T.; Fraser, Wesley C.; Jedicke, Robert; Lacerda, Pedro

2018-02-01

During the formation and evolution of the Solar System, significant numbers of cometary and asteroidal bodies were ejected into interstellar space1,2. It is reasonable to expect that the same happened for planetary systems other than our own. Detection of such interstellar objects would allow us to probe the planetesimal formation processes around other stars, possibly together with the effects of long-term exposure to the interstellar medium. 1I/2017 U1 `Oumuamua is the first known interstellar object, discovered by the Pan-STARRS1 telescope in October 2017 (ref. 3). The discovery epoch photometry implies a highly elongated body with radii of 200 × 20 m when a comet-like geometric albedo of 0.04 is assumed. The observable interstellar object population is expected to be dominated by comet-like bodies in agreement with our spectra, yet the reported inactivity of 'Oumuamua implies a lack of surface ice. Here, we report spectroscopic characterization of `Oumuamua, finding it to be variable with time but similar to organically rich surfaces found in the outer Solar System. We show that this is consistent with predictions of an insulating mantle produced by long-term cosmic ray exposure4. An internal icy composition cannot therefore be ruled out by the lack of activity, even though `Oumuamua passed within 0.25 au of the Sun.

Fungal bioremediation of the creosote-contaminated soil: influence of Pleurotus ostreatus and Irpex lacteus on polycyclic aromatic hydrocarbons removal and soil microbial community composition in the laboratory-scale study.

PubMed

Byss, Marius; Elhottová, Dana; Tříska, Jan; Baldrian, Petr

2008-11-01

The aim of this study was to determine the efficacy of selected basidiomycetes in the removing of polycyclic aromatic hydrocarbons (PAH) from the creosote-contaminated soil. Fungi Pleurotus ostreatus and Irpex lacteus were supplemented with creosote-contaminated (50-200 mg kg(-1) PAH) soil originating from a wood-preserving plant and incubated at 15 °C for 120 d. Either fungus degraded PAH with 4-6 aromatic rings more efficiently than the microbial community present initially in the soil. PAH removal was higher in P. ostreatus treatments (55-67%) than in I. lacteus treatments (27-36%) in general. P. ostreatus (respectively, I. lacteus) removed 86-96% (47-59%) of 2-rings PAH, 63-72% (33-45%) of 3-rings PAH, 32-49% (9-14%) of 4-rings PAH and 31-38% (11-13%) of 5-6-rings PAH. MIS (Microbial Identification System) Sherlock analysis of the bacterial community determined the presence of dominant Gram-negative bacteria (G-) Pseudomonas in the inoculated soil before the application of fungi. Complex soil microbial community was characterized by phospholipid fatty acids analysis followed by GC-MS/MS. Either fungus induced the decrease of bacterial biomass (G- bacteria in particular), but the soil microbial community was influenced by P. ostreatus in a different way than by I. lacteus. The bacterial community was stressed more by the presence of I. lacteus than P. ostreatus (as proved by the ratio of the fungal/bacterial markers and by the ratio of trans/cis mono-unsaturated fatty acids). Moreover, P. ostreatus stimulated the growth of Gram-positive bacteria (G+), especially actinobacteria and these results indicate the potential of the positive synergistic interaction of this fungus and actinobacteria in creosote biodegradation.

Spatial variation and sources of polycyclic aromatic hydrocarbons influenced by intensive land use in an urbanized river network of East China.

PubMed

Bi, Chunjuan; Wang, Xueping; Jia, Jinpu; Chen, Zhenlou

2018-06-15

The concentrations and distribution of polycyclic aromatic hydrocarbons (PAHs) in urbanized river networks are strongly influenced by intensive land use, industrial activities and population density. The spatial variations and their influencing factors of 16 priority PAHs were investigated in surface water, suspended particulate matter (SPM) and sediments among areas under different intensive land uses (industrial areas, agricultural areas, inner city, suburban towns and island areas) in the Shanghai river network, East China. Source apportionment was carried out using isomer ratios of PAHs and Positive Matrix Factorization (PMF). Total concentrations of 16 PAHs ranged from 105.2 to 400.5 ng/L, 108.1 to 1058.8 ng/L and 104.4 to 19,480.0 ng/g in water, SPM and sediments, respectively. The concentrations of PAHs in SPM and sediments varied significantly among areas (p < 0.05), with the highest concentrations in inner city characterized by highly intensive land use and high population density. The PAH concentrations in sediments were positively correlated with those in SPM and were more strongly correlated with black carbon than with total organic carbon, indicating a stronger influence of prolonged anthropogenic contamination than the recent surface input in sediments. Biomass and coal combustion contributed strongly to total PAHs, followed by natural gas combustion in water and SPM, and vehicular emissions in sediments. Vehicular emissions were the strongest contributors in SPM and sediments of the inner city, indicating the strong influence of vehicular transportation to PAHs pollution in the urbanized river network. Copyright © 2018 Elsevier B.V. All rights reserved.

Lung cancer risk by polycyclic aromatic hydrocarbons in a Mediterranean industrialized area.

PubMed

Cuadras, Anna; Rovira, Enric; Marcé, Rosa Maria; Borrull, Francesc

2016-11-01

This study focuses on characterizing the chronic risk assessment from inhalation of polycyclic aromatic hydrocarbons (PAHs) for people living near the largest chemical complex in the Mediterranean area. Eighteen PAHs were determined in the atmospheric gas and particle phases, counting PM 10 and total suspended particles. The lifetime lung cancer risk from PAH exposure was estimated, and the contribution was assessed by phases. The results obtained with the continuous lifetime scenario were compared with those obtained with different chronic scenarios. The estimated chronic risk was also compared with those reported in previous studies. PAHs were present at higher concentration in the gas phase (>84 %) with a major contribution of the most volatile PAHs, and an equitable distribution of heavy PAHs between gas and particle phases was observed. Petroleum combustion and traffic emissions were suggested as the main sources, but the influence of petrogenic sources cannot be ruled out. The estimated average lifetime lung cancer risk in this study ranged between 3.2 × 10 -5 and 4.3 × 10 -5 . The gas phase accounted for the most significant contribution to the total risk (>60 %). Fluoranthene (FluT), dibenzo(a,h)anthracene (DahA) and benzo(a)pyrene (BaP), as a whole, made the greatest contribution to the total risk (>80 %). BaP-bound PM 10 accounted for a small contribution of the total risk (10 %). Chronic exposures lower than total lifetime hours could even pose a risk >10 -5 . The results also showed that BaP-bound PM 10 , according to current legislation, may not be a good indicator of the real risk by PAH exposure. Concerning previous studies, the economic situation may have an impact on reducing the cancer risk by PAH inhalation.

Spectrum of PAH gene variants among a population of Han Chinese patients with phenylketonuria from northern China.

PubMed

Liu, Ning; Huang, Qiuying; Li, Qingge; Zhao, Dehua; Li, Xiaole; Cui, Lixia; Bai, Ying; Feng, Yin; Kong, Xiangdong

2017-10-05

Phenylketonuria (PKU), which primarily results from a deficiency of phenylalanine hydroxylase (PAH), is one of the most common inherited inborn errors of metabolism that impairs postnatal cognitive development. The incidence of various PAH variations differs by race and ethnicity. The aim of the present study was to characterize the PAH gene variants of a Han population from Northern China. In total, 655 PKU patients and their families were recruited for this study; each proband was diagnosed both clinically and biochemically with phenylketonuria. Subjects were sequentially screened for single-base variants and exon deletions or duplications within PAH via direct Sanger sequencing and multiplex ligation-dependent probe amplification (MLPA). A spectrum of 174 distinct PAH variants was identified: 152 previously documented variants and 22 novel variants. While single-base variants were distributed throughout the 13 exons, they were particularly concentrated in exons 7 (33.3%), 11 (14.2%), 6 (13.2%), 12 (11.0%), 3 (10.4%), and 5 (4.4%). The predominant variant was p.Arg243Gln (17.7%), followed by Ex6-96A > G (8.3%), p.Val399 = (6.4%), p.Arg53His (4.7%), p.Tyr356* (4.7%), p.Arg241Cys (4.6%), p.Arg413Pro (4.6%), p.Arg111* (4.4%), and c.442-1G > A (3.4%). Notably, two patients were also identified as carrying de novo variants. The composition of PAH gene variants in this Han population from Northern China was distinct from those of other ethnic groups. As such, the construction of a PAH gene variant database for Northern China is necessary to lay a foundation for genetic-based diagnoses, prenatal diagnoses, and population screening.

Characterization of Cultures Enriched from Acidic Polycyclic Aromatic Hydrocarbon-Contaminated Soil for Growth on Pyrene at Low pH▿

PubMed Central

Uyttebroek, Maarten; Vermeir, Steven; Wattiau, Pierre; Ryngaert, Annemie; Springael, Dirk

2007-01-01

Two polycyclic aromatic hydrocarbon (PAH)-contaminated soils of pH 2 were successfully used as inoculum to enrich cultures growing on phenanthrene and pyrene at different pHs, including pH 3. Selected pyrene-utilizing cultures obtained at pH 3, pH 5, and pH 7 were further characterized. All showed rapid [14C]pyrene mineralization at pH 3 and pH 5 and grew on pyrene at pH values ranging from 2 to 6. Eubacterial and mycobacterial 16S rRNA gene denaturing gradient gel electrophoresis fingerprinting and sequencing indicated that the cultures were dominated by a single bacterium closely related to Mycobacterium montefiorense, belonging to the slow-growing Mycobacterium sp. In contrast, a culture enriched on pyrene at pH 7 from a slightly alkaline soil sampled at the same site was dominated by Pseudomonas putida and a fast-growing Mycobacterium sp. The M. montefiorense-related species dominating the pyrene-utilizing cultures enriched from the acidic soils was also the dominant Mycobacterium species in the acidic soils. Our data indicate that a slow-growing Mycobacterium species is involved in PAH degradation in that culture and show that bacteria able to degrade high-molecular-weight PAHs at low pH are present in acidic PAH-contaminated soil. PMID:17369339

Mitochondrial DNA copy number and exposure to polycyclic aromatic hydrocarbons.

PubMed

Pavanello, Sofia; Dioni, Laura; Hoxha, Mirjam; Fedeli, Ugo; Mielzynska-Svach, Danuta; Baccarelli, Andrea A

2013-10-01

Increased mitochondrial DNA copy number (mtDNAcn) is a biologic response to mtDNA damage and dysfunction, predictive of lung cancer risk. Polycyclic aromatic hydrocarbons (PAHs) are established lung carcinogens and may cause mitochondrial toxicity. Whether PAH exposure and PAH-related nuclear DNA (nDNA) genotoxic effects are linked with increased mtDNAcn has never been evaluated. We investigated the effect of chronic exposure to PAHs on mtDNAcn in peripheral blood lymphocytes (PBLs) of 46 Polish male noncurrent smoking coke-oven workers and 44 matched controls, who were part of a group of 94 study individuals examined in our previous work. Subjects' PAH exposure and genetic alterations were characterized through measures of internal dose (urinary 1-pyrenol), target dose [anti-benzo[a]pyrene diolepoxide (anti-BPDE)-DNA adduct], genetic instability (micronuclei and telomere length), and DNA methylation (p53 promoter) in PBLs. mtDNAcn (MT/S) was measured using a validated real-time PCR method. Workers with PAH exposure above the median value (>3 μmol 1-pyrenol/mol creatinine) showed higher mtDNAcn [geometric means (GM) of 1.06 (unadjusted) and 1.07 (age-adjusted)] compared with controls [GM 0.89 (unadjusted); 0.89 (age-adjusted); (P = 0.029 and 0.016)], as well as higher levels of genetic and chromosomal [i.e., anti-BPDE-DNA adducts (P < 0.001), micronuclei (P < 0.001), and telomere length (P = 0.053)] and epigenetic [i.e., p53 gene-specific promoter methylation (P < 0.001)] alterations in the nDNA. In the whole study population, unadjusted and age-adjusted mtDNAcn was positively correlated with 1-pyrenol (P = 0.043 and 0.032) and anti-BPDE-DNA adducts (P = 0.046 and 0.049). PAH exposure and PAH-related nDNA genotoxicity are associated with increased mtDNAcn. The present study is suggestive of potential roles of mtDNAcn in PAH-induced carcinogenesis.

Mitochondrial DNA Copy Number and Exposure to Polycyclic Aromatic Hydrocarbons

PubMed Central

Pavanello, Sofia; Dioni, Laura; Hoxha, Mirjam; Fedeli, Ugo; Mielzynska-Švach, Danuta; Baccarelli, Andrea A.

2013-01-01

Background Increased mitochondrial DNA copy number (mtDNAcn) is a biological response to mtDNA damage and dysfunction predictive of lung cancer risk. Polycyclic aromatic hydrocarbons (PAHs) are established lung carcinogens and may cause mitochondrial toxicity. Whether PAH exposure and PAH-related nuclear DNA (nDNA) genotoxic effects are linked with increased mtDNAcn has never been evaluated. Methods We investigated the effect of chronic exposure to PAHs on mtDNAcn in peripheral blood lymphocytes (PBLs) of 46 Polish male non-current smoking cokeoven workers and 44 matched controls, who were part of a group of 94 study individuals examined in our previous work. Subjects PAH exposure and genetic alterations were characterized through measures of internal dose (urinary 1-pyrenol), target dose [anti-benzo[a]pyrene diolepoxide (anti-BPDE)-DNA adduct], genetic instability (micronuclei, MN and telomere length [TL]) and DNA methylation [p53 promoter] in PBLs. mtDNAcn (MT/S) was measured using a validated real-time PCR method. Results Workers with PAH exposure above the median value (>3 µmol 1-pyrenol/mol creatinine) showed higher mtDNAcn [geometric means (GM) of 1.06 (unadjusted) and 1.07 (age-adjusted)] compared to controls [GM 0.89 (unadjusted); 0.89 (age-adjusted)] (p=0.029 and 0.016), as well as higher levels of genetic and chromosomal [i.e. anti-BPDE-DNA adducts (p<0.001), MN (p<0.001) and TL (p=0.053)] and epigenetic [i.e., p53 gene-specific promoter methylation (p<0.001)] alterations in the nDNA. In the whole study population, unadjusted and age-adjusted mtDNAcn was positively correlated with 1-pyrenol (p=0.043 and 0.032) and anti-BPDE-DNA adducts (p=0.046 and 0.049). Conclusions PAH exposure and PAH-related nDNA genotoxicity are associated with increased mtDNAcn. Impact The present study is suggestive of potential roles of mtDNAcn in PAH-induced carcinogenesis. PMID:23885040

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

Accumulation of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs) in organic and mineral soil horizons from four U.S. remote forests.

PubMed

Obrist, Daniel; Zielinska, Barbara; Perlinger, Judith A

2015-09-01

We characterized distributions of 23 polycyclic aromatic hydrocarbons (Σ23PAH) and nine oxygenated PAHs (Σ9OPAH) in four remote forests. We observed highest Σ23PAH and Σ9OPAH concentrations in a coniferous forest in Florida, particularly in organic layers which we attributed to frequent prescribed burning. Across sites, Σ23PAH and Σ9OPAH concentrations strongly increased from surface to humidified organic layers (+1626%) where concentrations reached up to 584 ng g(-1). Concentrations in mineral soils were lower (average 37 ± 8 ng g(-1)); but when standardized per unit organic carbon (OC), PAH/OC and OPAH/OC ratios were at or above levels observed in organic layers. Accumulation in litter and soils (i.e., enrichment factors with depth) negatively correlated with octanol-water partition coefficients (Kow) and therefore was linked to water solubility of compounds. Concentrations of Σ9OPAHs ranged from 6 ± 6 ng g(-1) to 39 ± 25 ng g(-1) in organic layers, and from 3 ± 1 ng g(-1) to 11 ± 3 ng g(-1) in mineral soils, and were significantly and positively correlated to Σ23PAHs concentrations (r(2) of 0.90) across sites and horizons. While OPAH concentrations generally decreased from organic layers to mineral soil horizons, OPAH/OC ratios increased more strongly with depth compared to PAHs, in particular for anthrone, anthraquinone, fluorenone, and acenaphthenequinone. The strong vertical accumulation of OPAH relative to OC was exponentially and negatively correlated to C/N ratios (r(2)=0.67), a measure that often is used for tissue age. In fact, C/N ratios alone explained two-thirds of the variability in OPAH/OC ratios suggesting particularly high retention, sorption, and persistency of OPAHs in old, decomposed carbon fractions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Drug Treatment of Pulmonary Hypertension in Children

PubMed Central

Vorhies, Erika E; Ivy, David Dunbar

2013-01-01

Pulmonary arterial hypertension (PAH) is a rare disease in infants and children that is associated with significant morbidity and mortality. The disease is characterized by progressive pulmonary vascular functional and structural changes resulting in increased pulmonary vascular resistance and eventual right heart failure and death. In the majority of pediatric patients, PAH is idiopathic or associated with congenital heart disease and rarely is associated with other conditions such as connective tissue or thromboembolic disease. Although treatment of the underlying disease and reversal of advanced structural changes has not yet been achieved with current therapy, quality of life and survival have been improved significantly. Targeted pulmonary vasodilator therapies, including endothelin receptor antagonists, prostacyclin analogues and phosphodiesterase type 5 inhibitors, have demonstrated hemodynamic and functional improvement in children. The management of pediatric PAH remains challenging as treatment decisions continue to depend largely on results from evidence-based adult studies and the clinical experience of pediatric experts. This article reviews the current drug therapies and their use in the management of PAH in children. PMID:24114695

Mycophenolate mofetil attenuates pulmonary arterial hypertension in rats

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

Suzuki, Chihiro; Takahashi, Masafumi; Morimoto, Hajime

Pulmonary arterial hypertension (PAH) is characterized by abnormal proliferation of smooth muscle cells (SMCs), leading to occlusion of pulmonary arterioles, right ventricular (RV) hypertrophy, and death. We investigated whether mycophenolate mofetil (MMF), a potent immunosuppresssant, prevents the development of monocrotaline (MCT)-induced PAH in rats. MMF effectively decreased RV systolic pressure and RV hypertrophy, and reduced the medial thickness of pulmonary arteries. MMF significantly inhibited the number of proliferating cell nuclear antigen (PCNA)-positive cells, infiltration of macrophages, and expression of P-selectin and interleukin-6 on the endothelium of pulmonary arteries. The infiltration of T cells and mast cells was not affected bymore » MMF. In vitro experiments revealed that mycophenolic acid (MPA), an active metabolite of MMF, dose-dependently inhibited proliferation of human pulmonary arterial SMCs. MMF attenuated the development of PAH through its anti-inflammatory and anti-proliferative properties. These findings provide new insight into the potential role of immunosuppressants in the treatment of PAH.« less

Characterization of the particulate emissions from the BP Deepwater Horizon surface oil burns.

PubMed

Gullett, Brian K; Hays, Michael D; Tabor, Dennis; Wal, Randy Vander

2016-06-15

Sampling of the smoke plumes from the BP Deepwater Horizon surface oil burns led to the unintentional collection of soot particles on the sail of an instrument-bearing, tethered aerostat. This first-ever plume sampling from oil burned at an actual spill provided an opportunistic sample from which to characterize the particles' chemical properties for polycyclic aromatic hydrocarbons (PAHs), organic carbon, elemental carbon, metals, and polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) and physical properties for size and nanostructure. Thermal-optical analyses indicated that the particulate matter was 93% carbon with 82% being refractory elemental carbon. PAHs accounted for roughly 68μg/g of the PM filter mass and 5mg/kg oil burned, much lower than earlier laboratory based studies. Microscopy indicated that the soot is distinct from more common soot by its aggregate size, primary particle size, and nanostructure. PM-bound metals were largely unremarkable but PCDD/PCDF formation was observed, contrary to other's findings. Levels of lighter PCDD/PCDF and PAH compounds were reduced compared to historical samples, possibly due to volatilization or photo-oxidation. Published by Elsevier Ltd.

Sildenafil reduces signs of oxidative stress in pulmonary arterial hypertension: Evaluation by fatty acid composition, level of hydroxynonenal and heart rate variability

PubMed Central

Semen, Khrystyna; Yelisyeyeva, Olha; Jarocka-Karpowicz, Iwona; Kaminskyy, Danylo; Solovey, Lyubomyr; Skrzydlewska, Elzbieta; Yavorskyi, Ostap

2015-01-01

Pulmonary arterial hypertension (PAH) is a rare multifactorial disease with an unfavorable prognosis. Sildenafil therapy can improve functional capacity and pulmonary hemodynamics in PAH patients. Nowadays, it is increasingly recognized that the effects of sildenafil are pleiotropic and may also involve changes of the pro-/antioxidant balance, lipid peroxidation and autonomic control. In present study we aimed to assess the effects of sildenafil on the fatty acids (FAs) status, level of hydroxynonenal (HNE) and heart rate variability (HRV) in PAH patients. Patients with PAH were characterized by an increase in HNE and changes in the FAs composition with elevation of linoleic, oleic, docosahexanoic acids in phospholipids as well as reduced HRV with sympathetic predominance. Sildenafil therapy improved exercise capacity and pulmonary hemodynamics and reduced NT-proBNP level in PAH. Antioxidant and anti-inflammatory effects of sildenafil were noted from the significant lowering of HNE level and reduction of the phopholipid derived oleic, linoleic, docosahexanoic, docosapentanoic FAs. That was also associated with some improvement of HRV on account of the activation of the neurohumoral regulatory component. Incomplete recovery of the functional metabolic disorders in PAH patients may be assumed from the persistent increase in free FAs, reduced HRV with the sympathetic predominance in the spectral structure after treatment comparing to control group. The possibilities to improve PAH treatment efficacy through mild stimulation of free radical reactions and formation of hormetic reaction in the context of improved NO signaling are discussed. PMID:26654977

What Do We Know About the Ultraviolet Extinction Curve, Fifty Years After the Discovery of the Bump?

NASA Astrophysics Data System (ADS)

Clayton, Geoffrey C.

2012-05-01

It is almost 50 years since Ted Stecher reported the discovery of the 2175 A bump, and almost 25 years since CCM characterized the UV extinction curve as a one-parameter function of R(V), the ratio of total-to-selective extinction. Great strides have been made since then in laboratory, theory, and observation but many questions still remain. The bump is still an unidentified feature, and CCM is not a reliable guide to the wavelength dependence of dust extinction beyond the Milky Way. In fact, the average extinction curve of SMC dust, which has little or no evidence for a 2175 A bump, may be more common in extragalactic environments than Milky Way type dust. The UV extinction curve has been extended to the Lyman limit without any sign in a turnover in the far-UV rise. The old standbys, silicates, graphite, amorphous carbon, and PAH's are still the go-to grain types. But many questions remain about how global properties such as metallicity may lead to large variations in the extinction properties from one galaxy to another. Also of great interest is how dust grains are created, evolve and are destroyed, and in particular, what fraction comes from sources such as evolved stars and supernovae, and what fraction is grown in the ISM. I plan to summarize the role of laboratory and theory can play in better understanding the interstellar dust grains responsible UV extinction.

How anomalous is the interstellar extinction in NGC 3372, the Carina Nebula?

NASA Astrophysics Data System (ADS)

Tapia, M.; Roth, M.; Marraco, H.; Ruiz, M. T.

Near-infrared JHKL photometry of more than 200 stars in the open clusters Tr 14, Tr 15, Tr 16, Cr 228, and Cr 232 in the Carina Nebula is presented. By comparing these results with the available visual photometry and spectroscopy, it is found that the intracluster reddening is characterized, except in Tr 15, by a 'normal' extinction law for lambda greater than 0.5 micron, but is highly anomalous and variable in the U and B bands. Provisional two-color visual polarimetry suggests that the wavelength of maximum polarization is similar to that in the general interstellar medium. This behavior may be explained by the presence of intracluster interstellar grains 'processed' by the passage of shock waves, presumably associated with the violent history of Eta Carinae.

Characterization of Contaminant Migration Potential Through In-Place Sediment Caps

DTIC Science & Technology

2011-06-01

Miracle-Gro Lawn Products , Inc. (Marysville, OH). The peat moss was ground and sieved to 63-1000 µm before being used as an organic carbon...in the sediment. In the absence of a sorbent organic matter phase, the PAH mixture may be present as a separate oil phase that coats the sediment...for PAHs entrapped in the organic carbon of soil and sediment pores (Pignatello, J.J, 1990 and 1995; Schuth, Ch. and Grothwahl, P. et al. 1994; Ran

PAHs (Polycyclic Aromatic Hydrocarbons), Nitro-PAHs, Hopanes and Steranes Biomarkers in Sediments of Southern Lake Michigan, USA

PubMed Central

Huang, Lei; Chernyak, Sergei M.; Batterman, Stuart A.

2014-01-01

PAHs in the Great Lakes basin are of concern due to their toxicity and persistence in bottom sediments. Their nitro derivatives, nitro-PAHs (NPAHs), which can have stronger carcinogenic and mutagenic activity than parent PAHs, may follow similar transport routes and also are accumulated in sediments. Limited information exists regarding the current distribution, trends and loadings of these compounds, especially NPAHs, in Lake Michigan sediments. This study characterizes PAHs, NPAHs, and biomarkers steranes and hopanes in surface sediments collected at 24 offshore sites in southern Lake Michigan. The ΣPAH14 (sum of 14 compounds) ranged from 213 to 1291 ng/g dry weight (dw) across the sites, levels that are 2 to 10 times lower than those reported 20 to 30 years earlier. Compared to consensus-based sediment quality guidelines, PAH concentrations suggest very low risk to benthic organisms. The ΣNPAH5 concentration ranged from 2.9 to 18.6 ng/g dw, and included carcinogenic compounds 1-nitropyrene and 6-nitrochrysene. ΣSterane6 and ΣHopane5 concentrations ranged from 6.2 to 36 and 98 to 355 ng/g dw, respectively. Based on these concentrations, Lake Michigan is approximately receiving 11, 0.16, 0.25 and 3.6 metric tons per year (t/yr) of ΣPAH14, ΣNPAH5, ΣSterane6 and ΣHopane5, respectively. Maps of OC-adjusted concentrations display that concentrations decline with increasing off-shore distance. The major sources of PAHs and NPAHs are pyrogenic in nature, based on diagnostic ratios. Using chemical mass balance models, sources were apportioned to emissions from diesel engines (56±18%), coal power plants (27±14%), coal-tar pavement sealants (16±11%), and coke ovens (7±12%). The biomarkers identify a combination of petrogenic and biogenic sources, with the southern end of the lake more impacted by petroleum. This first report of NPAHs levels in sediments of Lake Michigan reveals several carcinogenic compounds at modest concentrations, and a need for further work to assess potential risks to aquatic organisms. PMID:24784742

Significance of Cytochrome P450 System Responses and Levels of Bile Fluorescent Aromatic Compounds in Marine Wildlife Following Oil Spills

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

Lee, Richard F.; Anderson, Jack W.

2005-07-01

The relationships among cytochrome P450 induction in marine wildlife species, levels of fluorescent aromatic compounds (FAC) in their bile, the chemical composition of the inducing compounds, the significance of the exposure pathway, and any resulting injury, as a consequence of exposure to crude oil following a spill, are reviewed. Fish collected after oil spills often show increases in cytochrome P450 system activity, cytochrome P4501A (CYP1A) and bile fluorescent aromatic compounds (FAC), that are correlated with exposure to polycyclic aromatic hydrocarbons (PAH) in the oil. There is also some evidence for increases in bile FAC and induction of cytochrome P450 inmore » marine birds and mammals after oil spills. However, when observed, increases in these exposure indicators are transitory and generally decrease to background levels within one year after the exposure. Laboratory studies have shown induction of cytochrome P450 systems occurs after exposure of fish to crude oil in water, sediment or food. Most of the PAH found in crude oil (dominantly 2- and 3-ring PAH) are not strong inducers of cytochrome P450. Exposure to the 4-ring chrysenes or the photooxidized products of the PAH may account for the cytochrome P450 responses in fish collected from oil-spill sites. The contribution of non-spill background PAH, particularly combustion-derived (pyrogenic) PAH, to bile FAC and cytochrome P450 system responses can be confounding and needs to be considered when evaluating oil spill effects. The ubiquity of pyrogenic PAH makes it important to fully characterize all sources of PAH, including PAH from natural resources, e.g. retene, in oil spill studies. In addition, such parameters as species, sex, age, ambient temperature and season need to be taken into account. While increases in fish bile FAC and cytochrome P450 system responses, can together, be sensitive general indicators of PAH exposure after an oil spill, there is little unequivocal evidence to suggest a linkage to higher order biological effects, e.g. toxicity, lesions, reproductive failure.« less

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.

Analysis of pure tar substances (polycyclic aromatic hydrocarbons) in the gas stream using ultraviolet visible (UV-Vis) spectroscopy and multivariate curve resolution (MCR).

PubMed

Weide, Tobias; Guschin, Viktor; Becker, Wolfgang; Koelle, Sabine; Maier, Simon; Seidelt, Stephan

2015-01-01

The analysis of tar, mostly characterized as polycyclic aromatic hydrocarbons (PAHs), describes a topic that has been researched for years. An online analysis of tar in the gas stream in particular is needed to characterize the tar conversion or formation in the biomass gasification process. The online analysis in the gas is carried out with ultraviolet-visible (UV-Vis) spectroscopy (190-720 nm). This online analysis is performed with a measuring cell developed by the Fraunhofer Institute for Chemical Technology (ICT). To this day, online tar measurements using UV-Vis spectroscopy have not been carried out in detail. Therefore, PAHs are analyzed as follows. The measurements are split into different steps. The first step to prove the online method is to vaporize single tar substances. These experiments show that a qualitative analysis of PAHs in the gas stream with the used measurement setup is possible. Furthermore, it is shown that the method provides very exact results, so that a differentiation of various PAHs is possible. The next step is to vaporize a PAH mixture. This step consists of vaporizing five pure substances almost simultaneously. The interpretation of the resulting data is made using a chemometric interpretation method, the multivariate curve resolution (MCR). The verification of the calculated results is the main aim of this experiment. It has been shown that the tar mixture can be analyzed qualitatively and quantitatively (in arbitrary units) in detail using the MCR. Finally it is the main goal of this paper to show the first steps in the applicability of the UV-Vis spectroscopy and the measurement setup on online tar analysis in view of characterizing the biomass gasification process. Due to that, the gasification plant (at the laboratory scale), developed and constructed by the Fraunhofer ICT, has been used to vaporize these substances. Using this gasification plant for the experiments enables the usage of the measurement setup also for the spectroscopic analysis of the tar formation during the biomass gasification.

Summary of Research/Publications

NASA Technical Reports Server (NTRS)

1997-01-01

Summary of research/publications include:(1) Comment on broadening of water microwave lines by collisions with helium atoms; (2) Calculations of ion-molecule deuterium fractionation reactions involving HD; (3) Ab initio predictions on the rotational spectra of carbon-chain carbene molecules; (4) Theoretical IR spectra of ionized naphthalene; (5) Improved collisional excitation rates for interstellar water; (6) Calculations on the competition between association and reaction for C3H+ + H2; (7) Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons: effect of ionization; (8) Calculations concerning interstellar isomeric abundance ratios for C3H and C3H2; (9) New calculations on the ion-molecule processes C2H2+ + H2 C2H3+ + H and C2H2+ + H2 C2H4+; (10) Anisotropic rigid rotor potential energy function for H2O-H2; (11) A correlated ab initio study of linear carbon-chain radicals CnH (n=2-7); (12) Ab initio characterization of MgCCH, MgCCH+, and MgC2 and pathways to their formation in the interstellar medium; (13) Why HOC+ is detectable in interstellar clouds: The rate of the reaction between HOC+ and H2; (14) A correlated ab initio study of the X 2A 1 and A 2E states of MgCH3; (15) On the stability of interstellar carbon clusters: The rate of the reaction between C3 and O; and (16) The rate of the reaction between CN and C2H2 at interstellar temperatures.

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.

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.;

Characterization Of Contaminant Migration Potential In The Vicinity Of An In-Place Sand Cap

EPA Science Inventory

This study characterized the chemical transport potential of polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPHs) in the vicinity of a sand cap placed in the nearshore zone of a tidal marine embayment. Groundwater seepage was investigated along the per...

Proteomic Characterization of Plasmid pLA1 for Biodegradation of Polycyclic Aromatic Hydrocarbons in the Marine Bacterium, Novosphingobium pentaromativorans US6-1

PubMed Central

Yun, Sung Ho; Choi, Chi-Won; Lee, Sang-Yeop; Lee, Yeol Gyun; Kwon, Joseph; Leem, Sun Hee; Chung, Young Ho; Kahng, Hyung-Yeel; Kim, Sang Jin; Kwon, Kae Kyoung; Kim, Seung Il

2014-01-01

Novosphingobium pentaromativorans US6-1 is a halophilic marine bacterium able to degrade polycyclic aromatic hydrocarbons (PAHs). Genome sequence analysis revealed that the large plasmid pLA1 present in N. pentaromativorans US6-1 consists of 199 ORFs and possess putative biodegradation genes that may be involved in PAH degradation. 1-DE/LC-MS/MS analysis of N. pentaromativorans US6-1 cultured in the presence of different PAHs and monocyclic aromatic hydrocarbons (MAHs) identified approximately 1,000 and 1,400 proteins, respectively. Up-regulated biodegradation enzymes, including those belonging to pLA1, were quantitatively compared. Among the PAHs, phenanthrene induced the strongest up-regulation of extradiol cleavage pathway enzymes such as ring-hydroxylating dioxygenase, putative biphenyl-2,3-diol 1,2-dioxygenase, and catechol 2,3-dioxygenase in pLA1. These enzymes lead the initial step of the lower catabolic pathway of aromatic hydrocarbons through the extradiol cleavage pathway and participate in the attack of PAH ring cleavage, respectively. However, N. pentaromativorans US6-1 cultured with p-hydroxybenzoate induced activation of another extradiol cleavage pathway, the protocatechuate 4,5-dioxygenase pathway, that originated from chromosomal genes. These results suggest that N. pentaromativorans US6-1 utilizes two different extradiol pathways and plasmid pLA1 might play a key role in the biodegradation of PAH in N. pentaromativorans US6-1. PMID:24608660

Chemical and toxicological characterization of sediments along a Colombian shoreline impacted by coal export terminals.

PubMed

Caballero-Gallardo, Karina; Guerrero-Castilla, Angelica; Johnson-Restrepo, Boris; de la Rosa, Jesus; Olivero-Verbel, Jesus

2015-11-01

Extraction, transport and utilization of coal spread out coal dust. Nowadays, Colombia is an important producer of this mineral in South America, being the Santa Marta area one of the largest coal exporting ports in the country. The aim of this work was to assess the pollutants levels and toxicity of shoreline sediments from this place. 16 PAHs and 46 elements were measured in nine locations during dry and rainy seasons. HepG2 cells were exposed to 1% sediment extracts and mRNA expression evaluated for selected genes. PAHs levels were greater during the rainy season. The highest ∑PAHs (89.9 ng g(-1)) appeared at a site located around 300 m far from the coast line at close proximity to the area where coal is loaded into cargo vessels for international shipments, being naphthalene the most abundant PAH. At Santa Marta Bay port, ∑PAHs were 62.8 ng g(-1) and 72.8 ng g(-1) for dry and rainy seasons, respectively, with greatest levels for fluoranthene. Based on sediment standards, most stations have poor condition regarding Cr, but moderate contamination on Cu, Pb and Zn. Sediments from the port and coal transport sites, the most polluted by PAHs and metals, induced CYP1A1 and NQO1 during the dry season. Data showed the sediments from this shoreline have bioactive chemicals that determine their toxicological profile. Copyright © 2015 Elsevier Ltd. All rights reserved.

A founder EIF2AK4 mutation causes an aggressive form of pulmonary arterial hypertension in Iberian Gypsies.

PubMed

Tenorio, J; Navas, P; Barrios, E; Fernández, L; Nevado, J; Quezada, C A; López-Meseguer, M; Arias, P; Mena, R; Lobo, J L; Alvarez, C; Heath, K; Escribano-Subías, P; Lapunzina, P

2015-12-01

Pulmonary arterial hypertension (PAH) is a pathological condition characterized by a persistent and progressive elevation of pulmonary vascular resistance with devastating consequences if untreated. In the past recent years, several genes have been related to PAH, however, the molecular defect remains unknown in a significant proportion of patients with familial PAH (∼20%). During the past few years, we have observed that PAH shows a particular behavior in Iberian Gypsies, with more aggressive course and frequently affecting multiple members of the same family. We studied five Gypsy families in whom at least one individual from each family developed a severe form of PAH and in whom no mutation had been identified in the common genes. We applied SNP-array-based homozygosity mapping in three families and obtained, among others, one of which included the gene EIF2AK4, recently reported in patients with PAH from group-1' pulmonary veno-occlusive disease (PVOD) and pulmonary capillary hemangiomatosis (PCH). Subsequently, we sequenced EIF2AK4 and found a homozygous mutation in all five families: c.3344C>T(p.P1115L). The majority of our patients required early lung transplantation. Hence, this mutation appeared with a more severe phenotype than previously reported for other EIF2AK4 mutations. The finding of this novel mutation is important for genetic counseling and calculation of population recurrence risks. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Identification of products formed during the heterogeneous nitration and ozonation of polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Cochran, Richard E.; Jeong, Haewoo; Haddadi, Shokouh; Fisseha Derseh, Rebeka; Gowan, Alexandra; Beránek, Josef; Kubátová, Alena

2016-03-01

The 3- and 4-ring polycyclic aromatic hydrocarbons (PAHs) are the most abundant of PAHs in air particulate matter (PM). Thus we have investigated heterogeneous oxidation of 3- and 4-ring PAHs in a small-scale flow reactor using quartz filter as a support. Four representative PAHs, anthracene, phenanthrene, pyrene, and fluoranthene, were exposed to either NO2, O3 or NO2+O3 (NO3/N2O5) with a goal to identify and attempt quantification of major product distribution. A combination of gas chromatography with mass spectrometry (GC-MS) with/without derivatization and liquid chromatography with high resolution MS (LC-HRMS) was used for identification. For the first time, a comprehensive characterization of a broad range of products enabled identifying ketone/diketone, aldehyde, hydroxyl, and carboxylic acid PAH derivatives. Exposure to NO3/N2O5 (formed by reacting NO2 with O3, a more powerful reactant than either O3 or NO2) produced additional compounds not observed with either oxidant alone. Multiple isomers of nitrofluoranthene and, for the first time, nitrophenanthrene were identified. In addition hydroxy-nitro-PAH derivatives were observed for the reaction of anthracene with NO3/N2O5. Monitoring of specific common ions such as those of 176 and 205 m/z attributed to carbonyl phenanthrene and deprotonated phenanthrene ions respectively was shown to be a useful tool for identification of multiple pyrene oxidation products.

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

Cooke, Ilsa R.; Fayolle, Edith C.; Öberg, Karin I., E-mail: irc5zb@virginia.edu

CO{sub 2} ice is an important reservoir of carbon and oxygen in star- and planet-forming regions. Together with water and CO, CO{sub 2} sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO{sub 2} ice spectroscopy is a prerequisite to characterize CO{sub 2} interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO{sub 2} longitudinal optical (LO) phonon mode in pure CO{sub 2} ice and in CO{sub 2} ice mixtures with H{submore » 2}O, CO, and O{sub 2} components. We show that the LO phonon mode position is sensitive to the mixing ratio of various ice components of astronomical interest. In the era of the James Webb Space Telescope , this characteristic could be used to constrain interstellar ice compositions and morphologies. More immediately, LO phonon mode spectroscopy provides a sensitive probe of ice mixing in the laboratory and should thus enable diffusion measurements with higher precision than has been previously possible.« less

The effects of neat biodiesel and biodiesel and HVO blends in diesel fuel on exhaust emissions from a light duty vehicle with a diesel engine.

PubMed

Prokopowicz, Adam; Zaciera, Marzena; Sobczak, Andrzej; Bielaczyc, Piotr; Woodburn, Joseph

2015-06-16

The influence of fatty acid methyl esters (FAME) and hydrotreated vegetable oil (HVO) diesel blends on the exhaust emissions from a passenger car was examined. The impact of FAME for the cold urban phase (UDC) was increased CO and HC emissions, probably due to blend physical properties promoting incomplete combustion. The HVO blend caused the lowest CO and HC emissions for the UDC. NOx emissions did not change significantly with the fuel used, however the UDC was characterized by lower NOx emission for FAME blends. Particle emissions were highest with standard diesel. Emissions of carbonyl compounds increased as fuel biodiesel content increased, especially during the UDC. HVO in diesel fuel decreased carbonyl emissions. Formaldehyde and acetaldehyde were the most abundant carbonyl compounds in the exhaust gas. Total particle-bound PAH emissions were variable, the emission of heavier PAHs increased with blend biodiesel content. The HVO blend increased emission of lighter PAHs. Nitro-PAHs were identified only during the UDC and not for all blends; the highest emissions were measured for pure diesel. The results showed that emission of nitro-PAHs may be decreased to a greater extent by using biodiesel than using a HVO blend.

Knitting aromatic polymers for efficient solid-phase microextraction of trace organic pollutants.

PubMed

Liu, Shuqin; Hu, Qingkun; Zheng, Juan; Xie, Lijun; Wei, Songbo; Jiang, Ruifen; Zhu, Fang; Liu, Yuan; Ouyang, Gangfeng

2016-06-10

A series of knitting aromatic polymers (KAPs) were successfully synthesized using a simple one-step Friedel-Crafts alkylation of aromatic monomers and were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Then, as-synthesized KAPs with large surface areas, unique pore structures and high thermal stability were prepared as solid-phase microextraction (SPME) coatings that exhibited good extraction abilities for a series of benzene compounds (i.e., benzene, toluene, ethylbenzene and m-xylene, which are referred to as BTEX) and polycyclic aromatic hydrocarbons (PAHs). Under the optimized conditions, the methodologies established for the determination of BTEX and PAHs using the KAPs-triPB and KAPs-B coatings, respectively, possessed wide linear ranges, low limits of detection (LODs, 0.10-1.13ngL(-1) for BTEX and 0.05-0.49ngL(-1) for PAHs) and good reproducibility. Finally, the proposed methods were successfully applied to the determination of BTEX and PAHs in environmental water samples, and satisfactory recoveries (93.6-124.2% for BTEX and 77.2-113.3% for PAHs) were achieved. This study provides a benchmark for exploiting novel microporous organic polymers (MOPs) for SPME applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets.

PubMed

Wang, Jun; Chen, Zaiming; Chen, Baoliang

2014-05-06

The adsorption of naphthalene, phenanthrene, and pyrene onto graphene (GNS) and graphene oxide (GO) nanosheets was investigated to probe the potential adsorptive sites and molecular mechanisms. The microstructure and morphology of GNS and GO were characterized by elemental analysis, XPS, FTIR, Raman, SEM, and TEM. Graphene displayed high affinity to the polycyclic aromatic hydrocarbons (PAHs), whereas GO adsorption was significantly reduced after oxygen-containing groups were attached to GNS surfaces. An unexpected peak was found in the curve of adsorption coefficients (Kd) with the PAH equilibrium concentrations. The hydrophobic properties and molecular sizes of the PAHs affected the adsorption of G and GO. The high affinities of the PAHs to GNS are dominated by π-π interactions to the flat surface and the sieving effect of the powerful groove regions formed by wrinkles on GNS surfaces. In contrast, the adsorptive sites of GO changed to the carboxyl groups attaching to the edges of GO because the groove regions disappeared and the polar nanosheet surfaces limited the π-π interactions. The TEM and SEM images initially revealed that after loading with PAH, the conformation and aggregation of GNS and GO nanosheets dramatically changed, which explained the observations that the potential adsorption sites of GNS and GO were unusually altered during the adsorption process.

Cancer risk from incidental ingestion exposures to PAHs associated with coal-tar-sealed pavement

USGS Publications Warehouse

Williams, E. Spencer; Mahler, Barbara J.; Van Metre, Peter C.

2012-01-01

Recent (2009-10) studies documented significantly higher concentrations of polycyclic aromatic hydrocarbons (PAHs) in settled house dust in living spaces and soil adjacent to parking lots sealed with coal-tar-based products. To date, no studies have examined the potential human health effects of PAHs from these products in dust and soil. Here we present the results of an analysis of potential cancer risk associated with incidental ingestion exposures to PAHs in settings near coal-tar-sealed pavement. Exposures to benzo[a]pyrene equivalents were characterized across five scenarios. The central tendency estimate of excess cancer risk resulting from lifetime exposures to soil and dust from nondietary ingestion in these settings exceeded 1 × 10–4, as determined using deterministic and probabilistic methods. Soil was the primary driver of risk, but according to probabilistic calculations, reasonable maximum exposure to affected house dust in the first 6 years of life was sufficient to generate an estimated excess lifetime cancer risk of 6 × 10–5. Our results indicate that the presence of coal-tar-based pavement sealants is associated with significant increases in estimated excess lifetime cancer risk for nearby residents. Much of this calculated excess risk arises from exposures to PAHs in early childhood (i.e., 0–6 years of age).

Key high molecular weight PAH-degrading bacteria in a soil consortium enriched using a sand-in-liquid microcosm system.

PubMed

Tauler, Margalida; Vila, Joaquim; Nieto, José María; Grifoll, Magdalena

2016-04-01

A novel biphasic system containing mineral medium and sand coated with a biologically weathered creosote-PAH mixture was developed to specifically enrich the high molecular weight polycyclic aromatic hydrocarbon (HMW PAH)-degrading community from a creosote-polluted soil. This consortium (UBHP) removed 70% of the total HMW PAHs and their alkyl-derivatives in 12 weeks. Based on a combined culture-dependent/independent approach, including clone library analysis, detection of catabolic genes, metabolomic profiles, and characterization of bacterial isolates, 10 phylotypes corresponding to five major genera (Sphingobium, Sphingomonas, Achromobacter, Pseudomonas, and Mycobacterium) were pointed out as key players within the community. In response to exposure to different single PAHs, members of sphingomonads were associated to the utilization of phenanthrene, fluoranthene, benzo[a]anthracene, and chrysene, while the degradation of pyrene was mainly associated to low-abundance mycobacteria. In addition to them, a number of uncultured phylotypes were detected, being of special relevance a group of Gammaproteobacteria closely related to a group previously associated with pyrene degradation that were here related to benzo(a)anthracene degradation. The overall environmental relevance of these phylotypes was confirmed by pyrosequencing analysis of the microbial community shift in the creosote-polluted soil during a lab-scale biostimulation.

Non-suppressive regulatory T cell subset expansion in pulmonary arterial hypertension.

PubMed

Sada, Yoshiharu; Dohi, Yoshihiro; Uga, Sayuri; Higashi, Akifumi; Kinoshita, Hiroki; Kihara, Yasuki

2016-08-01

Regulatory T cells (Tregs) have been reported to play a pivotal role in the vascular remodeling of pulmonary arterial hypertension (PAH). Recent studies have revealed that Tregs are heterogeneous and can be characterized by three phenotypically and functionally different subsets. In this study, we investigated the roles of Treg subsets in the pathogenesis of PAH in eight patients with PAH and 14 healthy controls. Tregs and their subsets in peripheral blood samples were analyzed by flow cytometry. Treg subsets were defined as CD4(+)CD45RA(+)FoxP3(low) resting Tregs (rTregs), CD4(+)CD45RA(-)FoxP3(high) activated Tregs (aTregs), and CD4(+)CD45RA(-)FoxP3(low) non-suppressive Tregs (non-Tregs). The proportion of Tregs among CD4(+) T cells was significantly higher in PAH patients than in controls (6.54 ± 1.10 vs. 3.81 ± 0.28 %, p < 0.05). Of the three subsets, the proportion of non-Tregs was significantly elevated in PAH patients compared with controls (4.06 ± 0.40 vs. 2.79 ± 0.14 %, p < 0.01), whereas those of rTregs and aTregs were not different between the two groups. Moreover, the expression levels of cytotoxic T lymphocyte antigen 4, a functional cell surface molecule, in aTregs (p < 0.05) and non-Tregs (p < 0.05) were significantly higher in PAH patients compared with controls. These results suggested the non-Treg subset was expanded and functionally activated in peripheral lymphocytes obtained from IPAH patients. We hypothesize that immunoreactions involving the specific activation of the non-Treg subset might play a role in the vascular remodeling of PAH.

Chemical signatures of the Anthropocene in the Clyde estuary, UK: sediment-hosted Pb, (207/206)Pb, total petroleum hydrocarbon, polyaromatic hydrocarbon and polychlorinated biphenyl pollution records.

PubMed

Vane, C H; Chenery, S R; Harrison, I; Kim, A W; Moss-Hayes, V; Jones, D G

2011-03-13

The sediment concentrations of total petroleum hydrocarbons (TPHs), polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), Pb and (207/206)Pb isotope ratios were measured in seven cores from the middle Clyde estuary (Scotland, UK) with an aim of tracking the late Anthropocene. Concentrations of TPHs ranged from 34 to 4386 mg kg(-1), total PAHs from 19 to 16,163 μg kg(-1) and total PCBs between less than 4.3 to 1217 μg kg(-1). Inventories, distributions and isomeric ratios of the organic pollutants were used to reconstruct pollutant histories. Pre-Industrial Revolution and modern non-polluted sediments were characterized by low TPH and PAH values as well as high relative abundance of biogenic-sourced phenanthrene and naphthalene. The increasing industrialization of the Clyde gave rise to elevated PAH concentrations and PAH isomeric ratios characteristic of both grass/wood/coal and petroleum and combustion (specifically petroleum combustion). Overall, PAHs had the longest history of any of the organic contaminants. Increasing TPH concentrations and a concomitant decline in PAHs mirrored the lessening of coal use and increasing reliance on petroleum fuels from about the 1950s. Thereafter, declining hydrocarbon pollution was followed by the onset (1950s), peak (1965-1977) and decline (post-1980s) in total PCB concentrations. Lead concentrations ranged from 6 to 631 mg kg(-1), while (207/206)Pb isotope ratios spanned 0.838-0.876, indicative of various proportions of 'background', British ore/coal and Broken Hill type petrol/industrial lead. A chronology was established using published Pb isotope data for aerosol-derived Pb and applied to the cores.

Succession of Phenotypic, Genotypic, and Metabolic Community Characteristics during In Vitro Bioslurry Treatment of Polycyclic Aromatic Hydrocarbon-Contaminated Sediments

PubMed Central

Ringelberg, David B.; Talley, Jeffrey W.; Perkins, Edward J.; Tucker, Samuel G.; Luthy, Richard G.; Bouwer, Edward J.; Fredrickson, Herbert L.

2001-01-01

Dredged harbor sediment contaminated with polycyclic aromatic hydrocarbons (PAHs) was removed from the Milwaukee Confined Disposal Facility and examined for in situ biodegradative capacity. Molecular techniques were used to determine the successional characteristics of the indigenous microbiota during a 4-month bioslurry evaluation. Ester-linked phospholipid fatty acids (PLFA), multiplex PCR of targeted genes, and radiorespirometry techniques were used to define in situ microbial phenotypic, genotypic, and metabolic responses, respectively. Soxhlet extractions revealed a loss in total PAH concentrations of 52%. Individual PAHs showed reductions as great as 75% (i.e., acenapthene and fluorene). Rates of 14C-PAH mineralization (percent/day) were greatest for phenanthrene, followed by pyrene and then chrysene. There was no mineralization capacity for benzo[a]pyrene. Ester-linked phospholipid fatty acid analysis revealed a threefold increase in total microbial biomass and a dynamic microbial community composition that showed a strong correlation with observed changes in the PAH chemistry (canonical r2 of 0.999). Nucleic acid analyses showed copies of genes encoding PAH-degrading enzymes (extradiol dioxygenases, hydroxylases, and meta-cleavage enzymes) to increase by as much as 4 orders of magnitude. Shifts in gene copy numbers showed strong correlations with shifts in specific subsets of the extant microbial community. Specifically, declines in the concentrations of three-ring PAH moieties (i.e., phenanthrene) correlated with PLFA indicative of certain gram-negative bacteria (i.e., Rhodococcus spp. and/or actinomycetes) and genes encoding for naphthalene-, biphenyl-, and catechol-2,3-dioxygenase degradative enzymes. The results of this study suggest that the intrinsic biodegradative potential of an environmental site can be derived from the polyphasic characterization of the in situ microbial community. PMID:11282603

Polycyclic aromatic hydrocarbon emission profiles and removal efficiency by electrostatic precipitator and wetfine scrubber in an iron ore sintering plant

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

Ettore Guerriero; Antonina Lutri; Rosanna Mabilia

2008-11-15

A monitoring campaign of polychlorinated dibenzo-p-dioxins and dibenzofurans, polyaromatic hydrocarbons (PAHs), and polychlorinated biphenyl was carried out in an Italian iron ore sintering plant by sampling the combustion gases at the electrostatic precipitator (ESP) outlet, at the Wetfine scrubber (WS) outlet, and by collecting the ESP dust. Few data are available on these micropollutants produced in iron ore sintering plants, particularly from Italian plants. This study investigates the PAH emission profiles and the removal efficiency of ESPs and WS. PAHs were determined at the stack, ESP outlet flue gases, and in ESP dust to characterize the emission profiles and themore » performance of the ESP and the WS for reducing PAH emission. The 11 PAHs monitored are listed in the Italian legislative decree 152/2006. The mean total PAH sum concentration in the stack flue gases is 3.96 {mu}g/N m{sup 3}, in ESP outlet flue gases is 9.73 {mu}g/N m{sup 3}, and in ESP dust is 0.53 {mu}g/g. Regarding the emission profiles, the most abundant compound is benzo(b)fluoranthene, which has a relative low BaP toxic equivalency factors (TEF) value, followed by dibenzo(a,l)pyrene, which has a very high BaP(TEF) value. The emission profiles in ESP dust and in the flue gases after the ESP show some changes, whereas the fingerprint in ESP and stack flue gases is very similar. The removal efficiency of the ESP and of WS on the total PAH concentration is 5.2 and 59.5%, respectively. 2 figs., 5 tabs.« less

Altered Right Ventricular Kinetic Energy Work Density and Viscous Energy Dissipation in Patients with Pulmonary Arterial Hypertension: A Pilot Study Using 4D Flow MRI.

PubMed

Han, Q Joyce; Witschey, Walter R T; Fang-Yen, Christopher M; Arkles, Jeffrey S; Barker, Alex J; Forfia, Paul R; Han, Yuchi

2015-01-01

Right ventricular (RV) function has increasingly being recognized as an important predictor for morbidity and mortality in patients with pulmonary arterial hypertension (PAH). The increased RV after-load increase RV work in PAH. We used time-resolved 3D phase contrast MRI (4D flow MRI) to derive RV kinetic energy (KE) work density and energy loss in the pulmonary artery (PA) to better characterize RV work in PAH patients. 4D flow and standard cardiac cine images were obtained in ten functional class I/II patients with PAH and nine healthy subjects. For each individual, we calculated the RV KE work density and the amount of viscous dissipation in the PA. PAH patients had alterations in flow patterns in both the RV and the PA compared to healthy subjects. PAH subjects had significantly higher RV KE work density than healthy subjects (94.7±33.7 mJ/mL vs. 61.7±14.8 mJ/mL, p = 0.007) as well as a much greater percent PA energy loss (21.1±6.4% vs. 2.2±1.3%, p = 0.0001) throughout the cardiac cycle. RV KE work density and percent PA energy loss had mild and moderate correlations with RV ejection fraction. This study has quantified two kinetic energy metrics to assess RV function using 4D flow. RV KE work density and PA viscous energy loss not only distinguished healthy subjects from patients, but also provided distinction amongst PAH patients. These metrics hold promise as imaging markers for RV function.

Invited papers presented to a workshop on thermodynamics and kinetics of dust formation in the space medium. [condensation, nucleation, and interstellar dust

NASA Technical Reports Server (NTRS)

Robertson, P. C.

1978-01-01

Abstracts of 25 papers relating to condensation processes in the early solar system are presented. Special emphasis is given to the transition of an initial vapor phase in the space medium, the characterization of condensation environments, and condensation processes in the space medium. The question of whether some fraction of the solar system solids (particularly exemplified by meteoritic solids) may be interstellar grains that gathered in the region of the proto-sun, rather than being products of local condensation is addressed.

Mineralogical, chemical and toxicological characterization of urban air particles.

PubMed

Čupr, Pavel; Flegrová, Zuzana; Franců, Juraj; Landlová, Linda; Klánová, Jana

2013-04-01

Systematic characterization of morphological, mineralogical, chemical and toxicological properties of various size fractions of the atmospheric particulate matter was a main focus of this study together with an assessment of the human health risks they pose. Even though near-ground atmospheric aerosols have been a subject of intensive research in recent years, data integrating chemical composition of particles and health risks are still scarce and the particle size aspect has not been properly addressed yet. Filling this gap, however, is necessary for reliable risk assessment. A high volume ambient air sampler equipped with a multi-stage cascade impactor was used for size specific particle collection, and all 6 fractions were a subject of detailed characterization of chemical (PAHs) and mineralogical composition of the particles, their mass size distribution and genotoxic potential of organic extracts. Finally, the risk level for inhalation exposure associated to the carcinogenic character of the studied PAHs has been assessed. The finest fraction (<0.45 μm) exhibited the highest mass, highest active surface, highest amount of associated PAHs and also highest direct and indirect genotoxic potentials in our model air sample. Risk assessment of inhalation scenario indicates the significant cancer risk values in PM 1.5 size fraction. This presented new approach proved to be a useful tool for human health risk assessment in the areas with significant levels of air dust concentration. Copyright © 2013 Elsevier Ltd. All rights reserved.

An interpretation of Mariner 10 helium /584 A/ and hydrogen /1216 A/ interplanetary emission observations

NASA Technical Reports Server (NTRS)

Ajello, J. M.

1978-01-01

Measurements of the interplanetary emissions of both He(584 A) and H(1216 A) on January 28, 1974, a time of solar minimum, are reported and discussed. An analysis of the Mariner 10 ultraviolet spectrometer data shows that a simultaneous measurement of both emissions results in a self-consistent determination of the physical properties of the interstellar wind. With the aid of a model the number densities of helium and hydrogen outside the solar system were found to be 0.008 + or - 0.003/cu cm and 0.04 (+0.03, -0.02)/cu cm, respectively, which indicates a He/H ratio of 0.20 (+0.30, -0.13). Values characterizing the helium cone, interstellar wind temperature, effective lifetime of hydrogen atoms in the solar system, and downstream direction of the interstellar wind are presented.

Bioremediation of a tropical clay soil contaminated with diesel oil.

PubMed

Chagas-Spinelli, Alessandra C O; Kato, Mario T; de Lima, Edmilson S; Gavazza, Savia

2012-12-30

The removal of polyaromatic hydrocarbons (PAH) in tropical clay soil contaminated with diesel oil was evaluated. Three bioremediation treatments were used: landfarming (LF), biostimulation (BS) and biostimulation with bioaugmentation (BSBA). The treatment removal efficiency for the total PAHs differed from the efficiencies for the removal of individual PAH compounds. In the case of total PAHs, the removal values obtained at the end of the 129-day experimental period were 87%, 89% and 87% for LF, BS and BSBA, respectively. Thus, the efficiency was not improved by the addition of nutrients and microorganisms. Typically, two distinct phases were observed. A higher removal rate occurred in the first 17 days (P-I) and a lower rate occurred in the last 112 days (P-II). In phase P-I, the zero-order kinetic parameter (μg PAH g(-1) soil d(-1)) values were similar (about 4.6) for all the three treatments. In P-II, values were also similar but much lower (about 0.14). P-I was characterized by a sharp pH decrease to less than 5.0 for the BS and BSBA treatments, while the pH remained near 6.5 for LF. Concerning the 16 individual priority PAH compounds, the results varied depending on the bioremediation treatment used and on the PAH species of interest. In general, compounds with fewer aromatic rings were better removed by BS or BSBA, while those with 4 or more rings were most effectively removed by LF. The biphasic removal behavior was observed only for some compounds. In the case of naphthalene, pyrene, chrysene, benzo[k]fluoranthene and benzo[a]pyrene, removal occurred mostly in the P-I phase. Therefore, the best degradation process for total or individual PAHs should be selected considering the target compounds and the local conditions, such as native microbiota and soil type. Copyright © 2012 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons and their derivatives in indoor and outdoor air in an eight-home study

NASA Astrophysics Data System (ADS)

Chuang, Jane C.; Mack, Gregory A.; Kuhlman, Michael R.; Wilson, Nancy K.

A pilot field study was performed in Columbus, OH, during the winter of 1986/1987. The objectives were to determine the feasibility of the use of a newly developed quiet sampler in indoor air sampling for particles and semivolatile organic compounds (SVOC) and to measure the concentrations of polycyclic aromatic hydrocarbons (PAH), PAH derivatives, and nicotine in air in selected residences. Eight homes were chosen for sampling on the basis of these characteristics: electric/gas heating system, electric/gas cooking appliances, and the absence/presence of environmental tobacco smoke (ETS). The indoor sampler was equipped with a quartz-fiber filter to collect particles followed by XAD-4 resin to trap SVOC. A PS-1 sampler with a similar sampling module was used outdoors. The indoor air was sampled in the kitchen and living room areas over two consecutive 8-h periods. The outdoor air was sampled concurrently with the indoor samples over a 16-h period. Fifteen PAH, five nitro-PAH, five oxygenated PAH, and three nitrogen heterocyclic compounds were determined in these samples. The most abundant PAH found indoors was naphthalene. The indoor concentrations of PAH derivatives were lower than those of their parent compounds. Average concentrations of all but three target compounds (naphthalene dicarboxylic acid anhydride, pyrene dicarboxylic acid anhydride, and 2-nitrofluoranthene) were higher indoors than outdoors. Environmental tobacco smoke was the most significant influence on indoor pollutant levels. Homes with gas heating systems had higher indoor pollutant levels than homes with electric heating systems. However, the true effects of heating and cooking systems were not characterized as accurately as the effects of ETS because of the small sample sizes and the lack of statistical significance for most pollutant differences in the absence of ETS. The concentrations of PAH marker compounds (phenanthrene, fluoranthene, and pyrene) correlated well with the concentrations of other target compounds. Quinoline and isoquinoline can be used to indicate indoor levels of ETS.

Composition of diesel exhaust with particular reference to particle bound organics including formation of artifacts.

PubMed

Lies, K H; Hartung, A; Postulka, A; Gring, H; Schulze, J

1986-01-01

For particulate emissions, standards were established by the US EPA in February 1980. Regulations limiting particulates from new light duty diesel vehicles are valid by model year 1982. The corresponding standards on a pure mass basis do not take into account any chemical character of the diesel particulate matter. Our investigation of the material composition shows that diesel particulates consist mainly of soot (up to 80% by weight) and adsorptively bound organics including polycyclic aromatic hydrocarbons (PAH). The qualitative and quantitative nature of hydrocarbon compounds associated with the particulates is dependent not only on the combustion parameters of the engine but also to an important degree on the sampling conditions when the particulates are collected (dilution ratio, temperature, filter material, sampling time etc.). Various methods for the analyses of PAH and their oxy- and nitro-derivatives are described including sampling, extraction, fractionation and chemical analysis. Quantitative comparison of PAH, nitro-PAH and oxy-PAH from different engines are given. For assessing mutagenicity of particulate matter, short-term biological tests are widely used. These biological tests often need a great amount of particulate matter requiring prolonged filter sampling times. Since it is well known that facile PAH oxidation can take place under the conditions used for sampling and analysis, the question rises if these PAH-derivates found in particle extracts partly or totally are produced during sampling (artifacts). Various results concerning nitro- and oxy-PAH are presented characterizing artifact formation as a minor problem under the conditions of the Federal Test Procedure. But results show that under other sampling conditions, e.g. electrostatic precipitation, higher NO2-concentrations and longer sampling times, artifact formation can become a bigger problem. The more stringent particulate standard of 0.2 g/mi for model years 1986 and 1987 respectively requires particulate trap technology. Preliminary investigations of the efficiency of ceramic filters used reveal that the reduction of the adsorptively bound organics is lower than the decrease of the solid carbonaceous fractions.

MicroRNA-138 and MicroRNA-25 Down-regulate Mitochondrial Calcium Uniporter, Causing the Pulmonary Arterial Hypertension Cancer Phenotype

PubMed Central

Hong, Zhigang; Chen, Kuang-Hueih; DasGupta, Asish; Potus, Francois; Dunham-Snary, Kimberly; Bonnet, Sebastien; Tian, Lian; Fu, Jennifer; Breuils-Bonnet, Sandra; Provencher, Steeve; Wu, Danchen; Mewburn, Jeffrey; Ormiston, Mark L.

2017-01-01

Rationale: Pulmonary arterial hypertension (PAH) is an obstructive vasculopathy characterized by excessive pulmonary artery smooth muscle cell (PASMC) proliferation, migration, and apoptosis resistance. This cancer-like phenotype is promoted by increased cytosolic calcium ([Ca2+]cyto), aerobic glycolysis, and mitochondrial fission. Objectives: To determine how changes in mitochondrial calcium uniporter (MCU) complex (MCUC) function influence mitochondrial dynamics and contribute to PAH’s cancer-like phenotype. Methods: PASMCs were isolated from patients with PAH and healthy control subjects and assessed for expression of MCUC subunits. Manipulation of the pore-forming subunit, MCU, in PASMCs was achieved through small interfering RNA knockdown or MCU plasmid-mediated up-regulation, as well as through modulation of the upstream microRNAs (miRs) miR-138 and miR-25. In vivo, nebulized anti-miRs were administered to rats with monocrotaline-induced PAH. Measurements and Main Results: Impaired MCUC function, resulting from down-regulation of MCU and up-regulation of an inhibitory subunit, mitochondrial calcium uptake protein 1, is central to PAH’s pathogenesis. MCUC dysfunction decreases intramitochondrial calcium ([Ca2+]mito), inhibiting pyruvate dehydrogenase activity and glucose oxidation, while increasing [Ca2+]cyto, promoting proliferation, migration, and fission. In PAH PASMCs, increasing MCU decreases cell migration, proliferation, and apoptosis resistance by lowering [Ca2+]cyto, raising [Ca2+]mito, and inhibiting fission. In normal PASMCs, MCUC inhibition recapitulates the PAH phenotype. In PAH, elevated miRs (notably miR-138) down-regulate MCU directly and also by decreasing MCU’s transcriptional regulator cAMP response element–binding protein 1. Nebulized anti-miRs against miR-25 and miR-138 restore MCU expression, reduce cell proliferation, and regress established PAH in the monocrotaline model. Conclusions: These results highlight miR-mediated MCUC dysfunction as a unifying mechanism in PAH that can be therapeutically targeted. PMID:27648837

Novel Approaches to Pulmonary Arterial Hypertension Drug Discovery

PubMed Central

Sung, Yon K.; Yuan, Ke; de Jesus Perez, Vinicio A.

2016-01-01

Introduction Pulmonary arterial hypertension (PAH) is a rare disorder associated with abnormally elevated pulmonary pressures that, if untreated, leads to right heart failure and premature death. The goal of drug development for PAH is to develop effective therapies that halt, or ideally, reverse the obliterative vasculopathy that results in vessel loss and obstruction of blood flow to the lungs. Areas Covered This review summarizes the current approach to candidate discovery in PAH and discusses the currently available drug discovery methods that should be implemented to prioritize targets and obtain a comprehensive pharmacological profile of promising compounds with well-defined mechanisms. Expert opinion To improve the successful identification of leading drug candidates, it is necessary that traditional pre-clinical studies are combined with drug screening strategies that maximize the characterization of biological activity and identify relevant off-target effects that could hinder the clinical efficacy of the compound when tested in human subjects. A successful drug discovery strategy in PAH will require collaboration of clinician scientists with medicinal chemists and pharmacologists who can identify compounds with an adequate safety profile and biological activity against relevant disease mechanisms. PMID:26901465

Molecular cloning and characterization of two novel human renal organic anion transporters (hOAT1 and hOAT3).

PubMed

Race, J E; Grassl, S M; Williams, W J; Holtzman, E J

1999-02-16

The cloned organic anion transporters from rat, mouse, and winter flounder (rOAT1, mOAT1, fROAT) mediate the coupled exchange of alpha-ketoglutarate with multiple organic anions, including p-aminohippurate (PAH). We have isolated two novel gene products from human kidney which bear significant homology to the known OATs and belong to the amphiphilic solute facilitator (ASF) family. The cDNAs, hOAT1 and hOAT3, encode for 550- and 568-amino-acid residue proteins, respectively. hOAT1 and hOAT3 mRNAs are expressed strongly in kidney and weakly in brain. Both genes map to chromosome 11 region q11.7. PAH uptake by Xenopus laevis oocytes injected with hOAT1 mRNA is increased 100-fold compared to water-injected oocytes. PAH uptake is chloride dependent and is not further increased by preincubation of oocytes in 5 mM glutarate. Uptake of PAH is inhibited by probenicid, alpha-ketoglutarate, bumetanide, furosemide, and losartan, but not by salicylate, urate, choline, amilioride, and hydrochlorothiazide. Copyright 1999 Academic Press.

Particle emission from heavy-duty engine fuelled with blended diesel and biodiesel.

PubMed

Martins, Leila Droprinchinski; da Silva Júnior, Carlos Roberto; Solci, Maria Cristina; Pinto, Jurandir Pereira; Souza, Davi Zacarias; Vasconcellos, Pérola; Guarieiro, Aline Lefol Nani; Guarieiro, Lílian Lefol Nani; Sousa, Eliane Teixeira; de Andrade, Jailson B

2012-05-01

In this study, particulate matter (PM) were characterized from a place impacted by heavy-duty vehicles (Bus Station) fuelled with diesel/biodiesel fuel blend (B3) in the city of Londrina, Brazil. Sixteen priority polycyclic aromatic hydrocarbons (PAH) concentrations were analyzed in the samples by their association with atmospheric PM, mass size distributions and major ions (fluorite, chloride, bromide, nitrate, phosphate, sulfate, nitrite, oxalate; fumarate, formate, succinate and acetate; lithium, sodium, potassium, magnesium, calcium and ammonium). Results indicate that major ions represented 21.2% particulate matter mass. Nitrate, sulfate, and ammonium, respectively, presented the highest concentration levels, indicating that biodiesel may also be a significant source for these ions, especially nitrate. Dibenzo[a,h]anthracene and indeno[1,2,3,-cd]pyrene were the main PAH found, and a higher fraction of PAH particles was found in diameters lower than 0.25 μm in Londrina bus station. The fine and ultrafine particles were dominant among the PM evaluated, suggesting that biodiesel decreases the total PAH emission. However, it does also increase the fraction of fine and ultrafine particles when compared to diesel.

Emission characteristics for polycyclic aromatic hydrocarbons from solid fuels burned in domestic stoves in rural China

PubMed Central

SHEN, Guofeng; TAO, Shu; Chen, Yuanchen; Zhang, Yanyan; Wei, Siye; Xue, Miao; Wang, Bin; WANG, Rong; LV, Yan; LI, Wei; SHEN, Huizhong; HUANG, Ye; CHEN, Han

2014-01-01

Emission characterization of polycyclic aromatic hydrocarbons (PAHs) from residential combustion of crop residues, woody material, coal, and biomass pellets in domestic stoves in rural China are compared in term of emission factors (EFs), influencing factors, composition profiles, isomer ratios and phase distributions. The EFs of PAHs vary by two orders of magnitude among fuel types suggesting that a detailed fuel categorization is useful in the development of an emission inventory and potential in emission abatement of PAHs by replacing dirty fuels with relatively cleaner ones. The influence of fuel moisture in biomass burning is non-linear. Biofuels with very low moisture display relatively high emissions as do fuels with very high moisture. Bituminous coals and brushwood yield relatively large fractions of high molecular PAHs. The emission factor of Benzo(a)pyrene equivalent quantity for raw bituminous coal is as high as 52 mg/kg, which is 1–2 orders of magnitude higher than the other fuels. For source diagnosis, high molecular weight isomers are more informative than low molecular weight ones and multiple ratios could be used together whenever possible. PMID:24245776

Signal transduction in the development of pulmonary arterial hypertension

PubMed Central

Malenfant, Simon; Neyron, Anne-Sophie; Paulin, Roxane; Potus, François; Meloche, Jolyane; Provencher, Steeve; Bonnet, Sébastien

2013-01-01

Pulmonary arterial hypertension (PAH) is a unique disease. Properly speaking, it is not a disease of the lung. It can be seen more as a microvascular disease occurring mainly in the lungs and affecting the heart. At the cellular level, the PAH paradigm is characterized by inflammation, vascular tone imbalance, pulmonary arterial smooth muscle cell proliferation and resistance to apoptosis and the presence of in situ thrombosis. At a clinical level, the aforementioned abnormal vascular properties alter physically the pulmonary circulation and ventilation, which greatly influence the right ventricle function as it highly correlates with disease severity. Consequently, right heart failure remains the principal cause of death within this cohort of patients. While current treatment modestly improve patients’ conditions, none of them are curative and, as of today, new therapies are lacking. However, the future holds potential new therapies that might have positive influence on the quality of life of the patient. This article will first review the clinical presentation of the disease and the different molecular pathways implicated in the pathobiology of PAH. The second part will review tomorrow's future putative therapies for PAH. PMID:24015329

Determination of polycyclic aromatic hydrocarbons, dibenzothiophene, and alkylated homologs in the lichen Hypogymnia physodes by gas chromatography using single quadrupole mass spectrometry and time-of-flight mass spectrometry.

PubMed

Studabaker, William B; Puckett, Keith J; Percy, Kevin E; Landis, Matthew S

2017-04-07

Development of the Athabasca Oil Sands Region in northeastern Alberta, Canada has contributed polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic compounds (PACs), which include alkyl PAHs and dibenzothiophenes, to the regional environment. A new analytical method was developed for quantification of PAHs and PACs in the epiphytic lichen bioindicator species Hypogymnia physodes for use in the development of receptor models for attribution of PAH and PAC concentrations to anthropogenic and natural emission sources. Milled lichens were extracted with cyclohexane, and extracts were cleaned on silica gel using automated solid phase extraction techniques. Quantitative analysis was performed by gas chromatography with selected ion monitoring (GC-SIM-MS) for PAHs, and by GC with time-of-flight mass spectrometry (GC-TOF-MS) for PACs. PACs were quantitated in groups using representative reference compounds as calibration standards. Analytical detection limits were ≤2.5ngg -1 for all individual compounds. Precision as measured by laboratory duplicates was variable; for individual analytes above 5ngg -1 the mean absolute difference between duplicates was typically <20%. Selection of single-analyte markers for source attribution should include consideration of data quality indicators. Use of TOF-MS to spectrally characterize PAC group constituents identified significant challenges for the accurate quantitation of PACs with more than two carbons in their side chain(s). Total PAH concentrations in lichen samples ranged from 12 to 482ngg -1 . Total PACs in each sample varied from a fraction of total PAHs to more than four times total PAHs. Results of our analyses of H. physodes are compared with other studies using other species of lichens as PAH receptors and with passive monitoring data using polyurethane foam (PUF) samplers in the Athabasca Oil Sands Region (AOSR). This study presents the first analytical methodology developed for the determination of PACs in an epiphytic lichen bioindicator species. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Identification of PAH Isomeric Structure in Cosmic Dust Analogs: The AROMA Setup

NASA Astrophysics Data System (ADS)

Sabbah, Hassan; Bonnamy, Anthony; Papanastasiou, Dimitris; Cernicharo, Jose; Martín-Gago, Jose-Angel; Joblin, Christine

2017-07-01

We developed a new analytical experimental setup called AROMA (Astrochemistry Research of Organics with Molecular Analyzer) that combines laser desorption/ionization techniques with ion trap mass spectrometry. We report here on the ability of the apparatus to detect aromatic species in complex materials of astrophysical interest and characterize their structures. A limit of detection of 100 femto-grams has been achieved using pure polycyclic aromatic hydrocarbon (PAH) samples, which corresponds to 2 × 108 molecules in the case of coronene (C24H12). We detected the PAH distribution in the Murchison meteorite, which is made of a complex mixture of extraterrestrial organic compounds. In addition, collision induced dissociation experiments were performed on selected species detected in Murchison, which led to the first firm identification of pyrene and its methylated derivatives in this sample.

Spectral fingerprinting of polycyclic aromatic hydrocarbons in high-volume ambient air samples by constant energy synchronous luminescence spectroscopy

USGS Publications Warehouse

Kerkhoff, M.J.; Lee, T.M.; Allen, E.R.; Lundgren, D.A.; Winefordner, J.D.

1985-01-01

A high-volume sampler fitted with a glass-fiber filter and backed by polyurethane foam (PUF) was employed to collect airborne particulate and gas-phase polycylic aromatic hydrocarbons (PAHs) in ambient air. Samples were collected from four sources representing a range of environmental conditions: gasoline engine exhaust, diesel engine exhaust, air near a heavily traveled interstate site, and air from a moderately polluted urban site. Spectral fingerprints of the unseparated particulate and gas-phase samples were obtained by constant energy synchronous luminescence spectroscopy (CESLS). Five major PAHs in the gas-phase extracts were characterized and estimated. The compatibility of a high-volume sampling method using polyurethane foam coupled with CESLS detection is explored for use as a screening technique for PAHs in ambient air. ?? 1985 American Chemical Society.

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.

The phn Genes of Burkholderia sp. Strain RP007 Constitute a Divergent Gene Cluster for Polycyclic Aromatic Hydrocarbon Catabolism

PubMed Central

Laurie, Andrew D.; Lloyd-Jones, Gareth

1999-01-01

Cloning and molecular ecological studies have underestimated the diversity of polycyclic aromatic hydrocarbon (PAH) catabolic genes by emphasizing classical nah-like (nah, ndo, pah, and dox) sequences. Here we report the description of a divergent set of PAH catabolic genes, the phn genes, which although isofunctional to the classical nah-like genes, show very low homology. This phn locus, which contains nine open reading frames (ORFs), was isolated on an 11.5-kb HindIII fragment from phenanthrene-degrading Burkholderia sp. strain RP007. The phn genes are significantly different in sequence and gene order from previously characterized genes for PAH degradation. They are transcribed by RP007 when grown at the expense of either naphthalene or phenanthrene, while in Escherichia coli the recombinant phn enzymes have been shown to be capable of oxidizing both naphthalene and phenanthrene to predicted metabolites. The locus encodes iron sulfur protein α and β subunits of a PAH initial dioxygenase but lacks the ferredoxin and reductase components. The dihydrodiol dehydrogenase of the RP007 pathway, PhnB, shows greater similarity to analogous dehydrogenases from described biphenyl pathways than to those characterized from naphthalene/phenanthrene pathways. An unusual extradiol dioxygenase, PhnC, shows no similarity to other extradiol dioxygenases for naphthalene or biphenyl oxidation but is the first member of the recently proposed class III extradiol dioxygenases that is specific for polycyclic arene diols. Upstream of the phn catabolic genes are two putative regulatory genes, phnR and phnS. Sequence homology suggests that phnS is a LysR-type transcriptional activator and that phnR, which is divergently transcribed with respect to phnSFECDAcAdB, is a member of the ς54-dependent family of positive transcriptional regulators. Reverse transcriptase PCR experiments suggest that this gene cluster is coordinately expressed and is under regulatory control which may involve PhnR and PhnS. PMID:9882667