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.

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

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.

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.

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.

PAH EMISSION AT THE BRIGHT LOCATIONS OF PDRs: THE grandPAH HYPOTHESIS

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

Andrews, H.; Tielens, A. G. G. M.; Boersma, C.

2015-07-01

The polycyclic aromatic hydrocarbon (PAH) emission observed in the Spitzer Infrared Spectrograph spectra of bright mid-IR locations of NGC 7023, NGC 2023, and NGC 1333 was analyzed. These objects show large variations in PAH band ratios when studied through spectral mapping. Nevertheless, the mid-IR spectra at these bright spots show a remarkably similar PAH emission. We used the NASA Ames PAH IR Spectroscopic Database to fit the observations and analyze the derived PAH populations. Our results show that PAH emission in the 5–15 μm range appears to be rather insensitive to variations of the radiation field. Similar PAH populations ofmore » neutral small to medium-sized PAHs (∼50%), with ionized species contributing in slightly less than 50%, provide very good fits. Analyzing the degeneracy of the results shows that subtle (but intrinsic) variations in the emission properties of individual PAHs lead to observable differences in the resulting spectra. On top of this, we found that variations of <30% in the PAH abundances would lead to noticeable spectral differences between the three photodissociation regions (PDRs). Therefore, PAH populations must be remarkably similar at these different lines of sight. To account for this, we suggest the concept of grandPAHs as a unique mixture of the most stable PAHs emitting at these spots. Using NGC 7023 as an example, the grandPAHs refer to the robust PAH population that results from the intense processing of PAHs at the border limit between the PDR and the molecular cloud, where, due to the UV radiation that destroys the PAH population, the abundance of PAHs starts decreasing as we move toward the star.« less

Underdetermined blind separation of three-way fluorescence spectra of PAHs in water

NASA Astrophysics Data System (ADS)

Yang, Ruifang; Zhao, Nanjing; Xiao, Xue; Zhu, Wei; Chen, Yunan; Yin, Gaofang; Liu, Jianguo; Liu, Wenqing

2018-06-01

In this work, underdetermined blind decomposition method is developed to recognize individual components from the three-way fluorescent spectra of their mixtures by using sparse component analysis (SCA). The mixing matrix is estimated from the mixtures using fuzzy data clustering algorithm together with the scatters corresponding to local energy maximum value in the time-frequency domain, and the spectra of object components are recovered by pseudo inverse technique. As an example, using this method three and four pure components spectra can be blindly extracted from two samples of their mixture, with similarities between resolved and reference spectra all above 0.80. This work opens a new and effective path to realize monitoring PAHs in water by three-way fluorescence spectroscopy technique.

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

Underdetermined blind separation of three-way fluorescence spectra of PAHs in water.

PubMed

Yang, Ruifang; Zhao, Nanjing; Xiao, Xue; Zhu, Wei; Chen, Yunan; Yin, Gaofang; Liu, Jianguo; Liu, Wenqing

2018-06-15

In this work, underdetermined blind decomposition method is developed to recognize individual components from the three-way fluorescent spectra of their mixtures by using sparse component analysis (SCA). The mixing matrix is estimated from the mixtures using fuzzy data clustering algorithm together with the scatters corresponding to local energy maximum value in the time-frequency domain, and the spectra of object components are recovered by pseudo inverse technique. As an example, using this method three and four pure components spectra can be blindly extracted from two samples of their mixture, with similarities between resolved and reference spectra all above 0.80. This work opens a new and effective path to realize monitoring PAHs in water by three-way fluorescence spectroscopy technique. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Developing the Infrared PAH Emission Bands Into Calibrated Probes of Astrophysical Conditions with The NASA Ames PAH IR Spectroscopic Database

NASA Astrophysics Data System (ADS)

Boersma, Christiaan

We propose to quantitatively calibrate the PAH band strength ratios that have been traditionally used as qualitative proxies of PAH properties and linking PAH observables with local astrophysical conditions, thus developing PAHs into quantitative probes of astronomical environments. This will culminate in a toolbox (calibration charts) that can be used by PAH experts and non-PAH experts alike to unlock the information hidden in PAH emission sources that are part of the Spitzer and ISO archives. Furthermore, the proposed work is critical to mine the treasure trove of information JWST will return as it will capture, for the first time, the complete mid-infrared (IR) PAH spectrum with fully resolved features, through a single aperture, and along single lines-of-sight; making it possible to fully extract the information contained in the PAH spectra. In short, the work proposed here represents a major step in enabling the astronomical PAH model to reach its full potential as a diagnostic of the physical and chemical conditions in objects spanning the Universe. Polycyclic aromatic hydrocarbons (PAHs), a common and important reservoir of accessible carbon across the Universe, play an intrinsic part in the formation of stars, planets and possibly even life itself. While most PAH spectra appear quite similar, they differ in detail and contain a wealth of untapped information. Thanks to recent advances in laboratory studies and computer-based calculations of PAH spectra, the majority of which have been made at NASA Ames, coupled with the astronomical modeling tools we have developed, we can interpret the spectral details at levels never before possible. This enables us to extract local physical conditions and track subtle changes in these conditions at levels previously impossible. Building upon the tools and paradigms developed as part of the publicly available NASA Ames PAH IR Spectroscopic Database (PAHdb; www.astrochem.org/pahdb/), the purpose of our proposed research is

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

THE NASA AMES POLYCYCLIC AROMATIC HYDROCARBON INFRARED SPECTROSCOPIC DATABASE: THE COMPUTED SPECTRA

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

Bauschlicher, C. W.; Ricca, A.; Boersma, C.

The astronomical emission features, formerly known as the unidentified infrared bands, are now commonly ascribed to polycyclic aromatic hydrocarbons (PAHs). The laboratory experiments and computational modeling done at the NASA Ames Research Center to create a collection of PAH IR spectra relevant to test and refine the PAH hypothesis have been assembled into a spectroscopic database. This database now contains over 800 PAH spectra spanning 2-2000 {mu}m (5000-5 cm{sup -1}). These data are now available on the World Wide Web at www.astrochem.org/pahdb. This paper presents an overview of the computational spectra in the database and the tools developed to analyzemore » and interpret astronomical spectra using the database. A description of the online and offline user tools available on the Web site is also presented.« less

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.

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

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).

The hydrogen coverage of interstellar PAHs

NASA Technical Reports Server (NTRS)

Barker, J. R.; Cohen, M.; Tielens, Alexander G. G. M.; Allamandola, Louis J.; Barker, J. R.; Barker, J. R.

1986-01-01

The rate at which the CH bond in interstellar Polycyclic Aromatic Hydrocarbons (PAHs) rupture due to the absorption of a UV photon has been calculated. The results show that small PAHs (less than or equal to 25 carbon atoms) are expected to be partially dehydrogenated in regions with intense UV fields, while large PAHs (greater than or equal to 25 atoms) are expected to be completely hydrogenated in those regions. Because estimate of the carbon content of interstellar PAHs lie in the range of 20 to 25 carbon atoms, dehydrogenation is probably not very important. Because of the absence of other emission features besides the 11.3 micrometer feature in ground-based 8 to 13 micrometer spectra, it has been suggested that interstellar PAHs are partially dehydrogenated. However, IRAS 8 to 22 micrometer spectra of most sources that show strong 7.7 and 11.2 micrometer emission features also show a plateau of emission extending from about 11.3 to 14 micrometer. Like the 11.3 micrometer feature, this new feature is attributed to the CH out of plane bending mode in PAHs. This new feature shows that interstellar PAHs are not as dehydrogenated as estimated from ground-based 8 to 13 micrometer spectra. It also constrains the molecular structure of interstellar PAHs. In particular, it seems that very condensed PAHs, such as coronene and circumcoronene, dominate the interstellar PAH mixture as expected from stability arguments.

Laboratory Gas-phase Infrared Spectra of Two Astronomically Relevant PAH Cations: Diindenoperylene, {{\\rm{C}}}_{32}{{\\rm{H}}}_{16}^{+} and Dicoronylene, {{\\rm{C}}}_{48}{{\\rm{H}}}_{20}^{+}

NASA Astrophysics Data System (ADS)

Zhen, Junfeng; Candian, Alessandra; Castellanos, Pablo; Bouwman, Jordy; Linnartz, Harold; Tielens, Alexander G. G. M.

2018-02-01

The first gas-phase infrared spectra of two isolated astronomically relevant and large polycyclic aromatic hydrocarbon (PAH) cations—diindenoperylene (DIP) and dicoronylene (DC)—in the 530–1800 cm‑1 (18.9‑5.6 μm) range—are presented. Vibrational band positions are determined for comparison to the aromatic infrared bands. The spectra are obtained via infrared multiphoton dissociation spectroscopy of ions stored in a quadrupole ion trap using the intense and tunable radiation of the free electron laser for infrared experiments (FELIX). DIP+ shows its main absorption peaks at 737 (13.57), 800 (12.50), 1001 (9.99), 1070 (9.35), 1115 (8.97), 1152 (8.68), 1278 (7.83), 1420 (7.04), and 1550 (6.45) cm‑1(μm), in good agreement with density functional theory (DFT) calculations that are uniformly scaled to take anharmonicities into account. DC+ has its main absorption peaks at 853 (11.72), 876 (11.42), 1032 (9.69), 1168 (8.56), 1300 (7.69), 1427 (7.01), and 1566 (6.39) cm‑1(μm), which also agree well with the scaled DFT results presented here. The DIP+ and DC+ spectra are compared with the prominent infrared features observed toward NGC 7023. This results both in matches and clear deviations. Moreover, in the 11.0–14.0 μm region, specific bands can be linked to CH out-of-plane (oop) bending modes of different CH edge structures in large PAHs. The molecular origin of these findings and their astronomical relevance are discussed.

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.

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

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

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

Molecular Spectroscopy in Astrophysics: Interstellar PAHs

NASA Technical Reports Server (NTRS)

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

2000-01-01

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

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.

PAH-Mineral Interactions. A Laboratory Approach to Astrophysical Catalysis

NASA Astrophysics Data System (ADS)

Adolfo Cruz Diaz, Gustavo; Mattioda, Andrew

2017-06-01

Polycyclic Aromatic Hydrocarbon (PAH) molecules carry the infrared emission features which dominate the spectra of most galactic and extragalactic sources. Our study investigates the chemical evolution, chemical properties, physical properties, thermal stability, and photostability of samples produced from the UV-irradiation of simulated mineral dust grains coated with aromatics and astrobiologically relevant ices, using infrared spectroscopy. We investigate the chemical evolution of aromatic organics via anhydrous (no H2O ice) and hydrous (H2O ice) mechanisms. The anhydrous mechanism involves UV-induced catalytic reactions between organics and dense-cloud mineral grains, whereas the hydrous mechanism incorporates H2O-rich ice mixtures with the minerals and organics. These investigations identify the chemical and physical interactions occurring between the organic species, the dust grains and water-rich ices.These laboratory simulations also generate observable IR spectroscopic parameters for future astronomical observations with infrared telescopes such as SOFIA and JWST as well as provide empirical parameters for input into astronomical models of the early stages of planetary formation. These studies give us a deeper understanding of the potential catalytic pathways mineral surfaces provide and a deeper understanding of the role of ice-organic compositions in the chemical reaction pathways and how these processes fit into the formation of new planetary systems.In order to achieve these goals we use the Harrick ‘Praying Mantis’ Diffuse Reflectance Accessory (DRIFTS), which allows FTIR measurements of dust samples under ambient conditions by measuring the light scattered by the dust sample. We have also incorporated a low -temperature reaction chamber permitting the DRIFTS measurements at low temperatures and high-vacuum. This set-up permits the analysis of the solid particles surfaces revealing the chemical species adsorbed as well as their chemical evolution

LABORATORY AND FIELD STUDIES TO EVALUATE RISKS TO LARVAL FISH FROM PHOTO-ACTIVATED TOXICITY OF PAHS

EPA Science Inventory

Hazard from photo-activation of PAHs has been well documented in aquatic organisms. Far less certain is the degree to which risk actually occurs in the field. This presentation outlines a series of laboratory and field experiments conducted to better understand the dosimetry and ...

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.

Single-laboratory validation of a GC/MS method for the determination of 27 polycyclic aromatic hydrocarbons (PAHs) in oils and fats.

PubMed

Rose, M; White, S; Macarthur, R; Petch, R G; Holland, J; Damant, A P

2007-06-01

A protocol for the measurement of 27 polycyclic aromatic hydrocarbons (PAHs) in vegetable oils by GC/MS has undergone single-laboratory validation. PAHs were measured in three oils (olive pomace, sunflower and coconut oil). Five samples of each oil (one unfortified, and four fortified at concentrations between 2 and 50 microg kg(-1)) were analysed in replicate (four times in separate runs). Two samples (one unfortified and one fortified at 2 microg kg(-1)) of five oils (virgin olive oil, grapeseed oil, toasted sesame oil, olive margarine and palm oil) were also analysed. The validation included an assessment of measurement bias from the results of 120 measurements of a certified reference material (coconut oil BCR CRM458 certified for six PAHs). The method is capable of reliably detecting 26 out of 27 PAHs, at concentration <2 microg kg(-1) which is the European Union maximum limit for benzo[a]pyrene, in vegetable oils, olive pomace oil, sunflower oil and coconut oil. Quantitative results were obtained that are fit for purpose for concentrations from <2 to 50 microg kg(-1) for 24 out of 27 PAHs in olive pomace oil, sunflower oil and coconut oil. The reliable detection of 2 microg kg(-1) of PAHs in five additional oils (virgin olive oil, grapeseed oil, toasted sesame oil, olive margarine and palm oil) has been demonstrated. The method failed to produce fit-for-purpose results for the measurement of dibenzo[a,h]pyrene, anthanthrene and cyclopenta[c,d]pyrene. The reason for the failure was the large variation in results. The likely cause was the lack of availability of (13)C isotope internal standards for these PAHs at the time of the study. The protocol has been shown to be fit-for-purpose and is suitable for formal validation by inter-laboratory collaborative study.

PAH Emission From ULIRGs: Evidence For Unusual Grain Properties?

NASA Astrophysics Data System (ADS)

Marshall, Jason A.; Armus, L.; Spoon, H. W. W.

2007-12-01

The tremendous power emerging from ultraluminous infrared galaxies (ULIRGs) is driven both by high levels of star-formation activity and AGN-related accretion. Observations of star-forming regions in the Milky Way and external star-forming galaxies provide evidence that the first of these energy generation mechanisms often also gives rise to emission from PAH molecules in the form of characteristic mid-IR features. Given the composite nature of ULIRGs, it is not surprising that many also exhibit significant emission from PAHs. Perhaps more surprising, however, is that some ULIRGs believed to be powered primarily by AGNs also show emission from PAHs, although typically at lower levels relative to their total dust output. To investigate the nature of the PAH emission from galaxies powered either by star-formation or AGN accretion alone, as well as emission from composite systems such as ULIRGs powered by both mechanisms, we present a detailed study of the PAH emission spectra from galaxies of each type. We use the CAFE spectral energy distribution decomposition software we have developed to derive and extinction correct the spectra of PAH emission from a sample of 100 galaxies with Spitzer/IRS observations, and use the results of this analysis to calculate the ratios of the various mid-IR PAH feature luminosities. In particular, we investigate to what extent these relative feature strengths vary as a function of the optical classification of galaxies, and we inquire into whether or not the derived feature strength ratios provide evidence for unusual grain properties in the extreme conditions within ULIRGs.

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

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.

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

Measurement of polycyclic aromatic hydrocarbon (PAHs) in interplanetary dust particles

NASA Technical Reports Server (NTRS)

Clemett, S. J.; Maechling, C. R.; Zare, R. N.; Swan, P. D.; Walker, R. M.

1993-01-01

We report here the first definitive measurements of specific organic molecules (polycyclic aromatic hydrocarbons (PAH's)) in interplanetary dust particles (IDP's). An improved version of the microbeam-two-step laser mass spectrometer was used for the analysis. Two IDP's gave similar mass spectra showing an abundance of PAH's. Control samples, including particles of probable terrestrial origin from the same stratospheric collector, gave either null results or quite different spectra. We conclude that the PAH's are probably indigenous to the IDP's and are not terrestrial contaminants. The instrument used to study the particles is a two-step laser mass spectrometer. Constituent neutral molecules of the sample are first desorbed with a pulsed infrared laser beam focussed to 40 micrometers. In the second step, PAH's in the desorbed plume are preferentially ionized by a pulsed UV laser beam. Resulting ions produced by resonant absorption are extracted into a reflectron time-of-flight mass spectrometer. This instrument has high spatial resolution, high ion transmission, unlimited mass range, and multichannel detection of all ion masses from a single laser shot.

Ensemble empirical mode decomposition based fluorescence spectral noise reduction for low concentration PAHs

NASA Astrophysics Data System (ADS)

Wang, Shu-tao; Yang, Xue-ying; Kong, De-ming; Wang, Yu-tian

2017-11-01

A new noise reduction method based on ensemble empirical mode decomposition (EEMD) is proposed to improve the detection effect for fluorescence spectra. Polycyclic aromatic hydrocarbons (PAHs) pollutants, as a kind of important current environmental pollution source, are highly oncogenic. Using the fluorescence spectroscopy method, the PAHs pollutants can be detected. However, instrument will produce noise in the experiment. Weak fluorescent signals can be affected by noise, so we propose a way to denoise and improve the detection effect. Firstly, we use fluorescence spectrometer to detect PAHs to obtain fluorescence spectra. Subsequently, noises are reduced by EEMD algorithm. Finally, the experiment results show the proposed method is feasible.

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

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

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

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

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

Tadalafil in idiopathic or heritable pulmonary arterial hypertension (PAH) compared to PAH associated with connective tissue disease.

PubMed

Galiè, Nazzareno; Denton, Christopher P; Dardi, Fabio; Manes, Alessandra; Mazzanti, Gaia; Li, Baohui; Varanese, Lucio; Esler, Anne; Harmon, Cathi; Palazzini, Massimiliano

2017-05-15

The primary objective of this post hoc analysis was to evaluate clinical outcomes of tadalafil in patients with pulmonary arterial hypertension (PAH) associated with connective tissue disease (CTD-PAH) compared with patients with idiopathic/heritable PAH (I/H-PAH) for primary and key secondary efficacy endpoints, and safety. This analysis included adult patients with CTD-PAH or I/H-PAH who participated in the PHIRST and PHIRST-2 studies. Patients were randomized 1:1:1:1:1 to tadalafil (2.5, 10, 20, or 40mg) or placebo in the PHIRST study and the majority of these patients were subsequently assigned 40mg in PHIRST-2. Patients taking 20mg in PHIRST without demonstrating clinical worsening continued on 20mg in PHIRST-2. Outcomes analyzed included 6MWD, WHO-FC, and incidence and time to first occurrence of clinical worsening. Safety was assessed through evaluation of adverse events (AEs), clinical laboratory data, electrocardiograms, and physical examinations. Increased 6MWD in PHIRST was maintained in both CTD-PAH and I/H-PAH subgroups for 52weeks. Patients with CTD-PAH tended to be older, were more likely female, had lower exercise capacity, were more likely to have clinical worsening, and experienced AEs more frequently than patients with I/H-PAH. The effect of tadalafil treatment in patients enrolled in both PHIRST studies was detectable for both I/H-PAH and CTD-PAH subgroups. In general, subgroup differences were modest. Patients with CTD-PAH may perform less well than patients with I/H-PAH in safety and efficacy measures in all treatment groups, which is similar to other studies demonstrating a worse prognosis for patients with CTD-PAH. Copyright © 2017. Published by Elsevier B.V.

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.

Infrared Spectra of Polycyclic Aromatic Hydrocarbons (PAHs)

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Bakes, E. L. O.

2000-01-01

We have computed the synthetic infrared spectra of some polycyclic aromatic hydrocarbons containing up to 54 carbon atoms. The species studied include ovalene, circumcoronene, dicoronylene, and hexabenzocoronene. We report spectra for anions, neutrals, cations, and multiply charged cations.

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.

Carbon in The Universe: PAHs and Clusters

NASA Technical Reports Server (NTRS)

Saykally, Richard J.

1997-01-01

Following the initial demonstration of this new technique (Science 265 1686 (1994)) and its application to a series of neutral PAHs which have been proposed as condidates for the UIRs (Nature 380, 227 (1996)), we have concentrated on two major aspects of this project. 1. Developing a detailed model for infrared emission spectra of a collection of highly excited PAH molecules, in which experimental bandshapes and temperature-dependent redshifts are used in conjunction with ab initio vibrational frequencies and intensities to simulate the UIR bands. This shows that a collection of nine different cations (as large as ovalene) reproduce the UIR features better than do a collection of the corresponding neutrals, but a detailed match with the UIRs is not obtained. 2. Construction of SPIRES apparatus for the study of PAH ion emission spectra. The design of this experiment is shown and described. Unfortunately a disasterous accident occurred just as we were preparing to start the testing of the ion apparatus. A vacuum implosion occurred, destroying the liquid He cooled monochromator. It has taken us nearly one full year to reconstruct this, and we arc only now in the final testing of the new system. We expect to try the ion experiments by the end of summer.

Laboratory spectra of C60 and related molecular structures

NASA Technical Reports Server (NTRS)

Janca, J.; Solc, M.; Vetesnik, M.

1994-01-01

The electronic spectra of fullerene structures in high frequency discharge are studied in the plasma chemistry laboratory of the Faculty of Science of Masaryk University in Brno. The ultraviolet and visual spectra are investigated in order to be compared with the diffuse interstellar bands and interpreted within the theory of quantum mechanics. The preliminary results of the study are presented here in the form of a poster.

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.

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.

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

Changes in PAH levels during production of rapeseed oil.

PubMed

Cejpek, K; Hajslová, J; Kocourek, V; Tomaniová, M; Cmolík, J

1998-07-01

The influence of technological operations during rapeseed oil production on polycyclic aromatic hydrocarbon (PAH) concentrations in by-products, intermediate and final oils was evaluated. The decrease of light PAHs, benz(a)anthracene and benzo(a)pyrene during processing of crude oil to the deodorized product was significant at the 95% confidence interval in most batches analysed. Deodorization and alkali-refining were the steps contributing most to the PAH decrease. The relationship between PAH levels in rapeseed (and consequently in refined oil) and the duration of storage period was studied. The contamination of raw material processed a short time after harvesting was significantly higher than that of the rapeseed stored in silos for several months. Analyses of rapeseed samples, which were re-purified in the laboratory, revealed that solid particles, which contaminate rapeseed during harvesting, initial treatment, transport and storage, contributed to PAH contamination to the extent of 36% (light PAHs) to 64% (heavy PAHs) on average. Further experiments demonstrated that PAHs in re-purified rapeseed were concentrated in the cuticular layer, because they were removed well from the whole seeds by simple rinsing with organic solvent in an ultrasonic bath without losses of rapeseed oil. Alternative expressions of total PAH contamination (e.g. various PAH groups and/or differently defined B(a)P toxic equivalents) are discussed and their effect on drawing conclusions about PAH elimination rate has been demonstrated.

Single photon infrared emission spectroscopy: a study of IR emission from UV laser excited PAHs between 3 and 15 micrometers

NASA Technical Reports Server (NTRS)

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

1998-01-01

Single-photon infrared emission spectroscopy (SPIRES) has been used to measure emission spectra from polycyclic aromatic hydrocarbons (PAHs). A supersonic free-jet expansion has been used to provide emission spectra of rotationally cold and vibrationally excited naphthalene and benzene. Under these conditions, the observed width of the 3.3-micrometers (C-H stretch) band resembles the bandwidths observed in experiments in which emission is observed from naphthalene with higher rotational energy. To obtain complete coverage of IR wavelengths relevant to the unidentified infrared bands (UIRs), UV laser-induced desorption was used to generate gas-phase highly excited PAHs. Lorentzian band shapes were convoluted with the monochromator-slit function in order to determine the widths of PAH emission bands under astrophysically relevant conditions. Bandwidths were also extracted from bands consisting of multiple normal modes blended together. These parameters are grouped according to the functional groups mostly involved in the vibration, and mean bandwidths are obtained. These bandwidths are larger than the widths of the corresponding UIR bands. However, when the comparison is limited to the largest PAHs studied, the bandwidths are slightly smaller than the corresponding UIR bands. These parameters can be used to model emission spectra from PAH cations and cations of larger PAHs, which are better candidate carriers of the UIRs.

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.

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.

The NASA Ames PAH IR Spectroscopic Database: Computational Version 3.00 with Updated Content and the Introduction of Multiple Scaling Factors

NASA Astrophysics Data System (ADS)

Bauschlicher, Charles W., Jr.; Ricca, A.; Boersma, C.; Allamandola, L. J.

2018-02-01

Version 3.00 of the library of computed spectra in the NASA Ames PAH IR Spectroscopic Database (PAHdb) is described. Version 3.00 introduces the use of multiple scale factors, instead of the single scaling factor used previously, to align the theoretical harmonic frequencies with the experimental fundamentals. The use of multiple scale factors permits the use of a variety of basis sets; this allows new PAH species to be included in the database, such as those containing oxygen, and yields an improved treatment of strained species and those containing nitrogen. In addition, the computed spectra of 2439 new PAH species have been added. The impact of these changes on the analysis of an astronomical spectrum through database-fitting is considered and compared with a fit using Version 2.00 of the library of computed spectra. Finally, astronomical constraints are defined for the PAH spectral libraries in PAHdb.

Mapping PAH sizes in NGC 7023 with SOFIA

NASA Astrophysics Data System (ADS)

Croiset, B. A.; Candian, A.; Berné, O.; Tielens, A. G. G. M.

2016-05-01

Context. NGC 7023 is a well-studied reflection nebula, which shows strong emission from polycyclic aromatic hydrocarbon (PAH) molecules in the form of aromatic infrared bands (AIBs). The spectral variations of the AIBs in this region are connected to the chemical evolution of the PAH molecules which, in turn, depends on the local physical conditions. Aims: Our goal is to map PAH sizes in NGC 7023 with respect to the location of the star. We focus on the north west (NW) photo-dissociation region (PDR) and the south PDR of NGC 7023 to understand the photochemical evolution of PAHs, using size as a proxy. Methods: We use the unique capabilities of the Stratospheric Observatory for Infrared Astronomy (SOFIA) to observe a 3.2' × 3.4' region of NGC 7023 at wavelengths that we observe with high spatial resolution (2.7'') at 3.3 and 11.2 μm. We compare the SOFIA images with existing images of the PAH emission at 8.0 μm (Spitzer), emission from evaporating very small grains (eVSG) extracted from Spitzer-IRS spectral cubes, the extended red emission (Hubble Space Telescope and Canadian French Hawaiian Telescope), and H2 (2.12 μm). We create maps of the 11.2/3.3 μm ratio to probe the morphology of the PAH size distribution and the 8.0/11.2 μm ratio to probe the PAH ionization. We make use of an emission model and of vibrational spectra from the NASA Ames PAH database to translate the 11.2/3.3 μm ratio to PAH sizes. Results: The 11.2/3.3 μm ratio map shows the smallest PAH concentrate on the PDR surface (H2 and extended red emission) in the NW and south PDR. We estimated that PAHs in the NW PDR bear, on average, a number of carbon atoms (Nc) of ~70 in the PDR cavity and ~50 at the PDR surface. In the entire nebula, the results reveal a factor of 2 variation in the size of the PAH. We relate these size variations to several models for the evolution of the PAH families when they traverse from the molecular cloud to the PDR. Conclusions: The high-resolution PAH size map

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.

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.

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

Excited State Trends in Bidirectionally Expanded Closed-Shell PAH and PANH Anions

PubMed Central

Moore, Megan M.; Lee, Timothy J.

2018-01-01

Some anions are known to exhibit excited states independent of external forces such as dipole moments and induced polarizabilities. Such states exist simply as a result of the stabilization of valence accepting orbitals whereby the binding energy of the extra electron is greater than the valence excitation energy. Closed-shell anions are interesting candidates for such transitions since their ground-state, spin-paired nature makes the anions more stable from the beginning. Consequently, this work shows the point beyond which deprotonated, closed-shell polycyclic aromatic hydrocarbons (PAHs) and those PAHs containing nitrogen heteroatoms (PANHs) will exhibit valence excited states. This behavior has already been demonstrated in some PANHs and for anistropically-extended PAHs. This work establishes a general trend for PAHs/PANHs of arbitrary size and directional extension, whether in one dimension or two. Once seven six-membered rings make up a PAH/PANH, valence excited states are present. For most classes of PAHs/PANHs, this number is closer to four. Even though most of these excited states are weak absorbers, the sheer number of PAHs present in various astronomical environments should make them significant contributors to astronomical spectra. PMID:27585793

Properties of Polycyclic Aromatic Hydrocarbons in the Northwest Photon Dominated Region of NGC 7023. I. PAH Size, Charge, Composition, and Structure Distribution

NASA Technical Reports Server (NTRS)

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

2013-01-01

Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer Infrared Spectrograph spectral map of the northwest photon dominated region (PDR) in NGC 7023 was analyzed exclusively using PAH spectra from the NASA Ames PAH IR Spectroscopic Database (www.astrochem.org/pahdb). The 5-15 micron spectrum at each pixel is fitted using a non-negative-least-squares fitting approach. The fits are of good quality, allowing decomposition of the PAH emission into four subclasses: size, charge, composition, and hydrogen adjacency (structure). Maps tracing PAH subclass distributions across the region paint a coherent astrophysical picture. Once past some 20 seconds of arc from HD 200775, the emission is dominated by the more stable, large, symmetric, compact PAH cations with smaller, neutral PAHs taking over along the lines-of-sight toward the more distant molecular cloud. The boundary between the PDR and the denser cloud material shows up as a distinct discontinuity in the breakdown maps. Noteworthy is the requirement for PANH cations to fit the bulk of the 6.2 and 11.0 micron features and the indication of PAH photo-dehydrogenation and fragmentation close to HD 200775. Decomposition of the spectral maps into "principal" subclass template spectra provides additional insight into the behavior of each subclass. However, the general applicability of this computationally more efficient approach is presently undetermined. This is the first time the spectra of individual PAHs are exclusively used to fit the 5-15 micron region and analyze the spatial behavior of the aromatic infrared bands, providing fundamental, new information about astronomical PAH subpopulations including their dependence on, and response to, changes in local conditions.

Properties of Polycyclic Aromatic Hydrocarbons in the Northwest Photon Dominated Region of NGC 7023. I. PAH Size, Charge, Composition, and Structure Distribution

NASA Astrophysics Data System (ADS)

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

2013-06-01

Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer Infrared Spectrograph spectral map of the northwest photon dominated region (PDR) in NGC 7023 was analyzed exclusively using PAH spectra from the NASA Ames PAH IR Spectroscopic Database (www.astrochem.org/pahdb). The 5-15 μm spectrum at each pixel is fitted using a non-negative-least-squares fitting approach. The fits are of good quality, allowing decomposition of the PAH emission into four subclasses: size, charge, composition, and hydrogen adjacency (structure). Maps tracing PAH subclass distributions across the region paint a coherent astrophysical picture. Once past some 20 seconds of arc from HD 200775, the emission is dominated by the more stable, large, symmetric, compact PAH cations with smaller, neutral PAHs taking over along the lines-of-sight toward the more distant molecular cloud. The boundary between the PDR and the denser cloud material shows up as a distinct discontinuity in the breakdown maps. Noteworthy is the requirement for PANH cations to fit the bulk of the 6.2 and 11.0 μm features and the indication of PAH photo-dehydrogenation and fragmentation close to HD 200775. Decomposition of the spectral maps into "principal" subclass template spectra provides additional insight into the behavior of each subclass. However, the general applicability of this computationally more efficient approach is presently undetermined. This is the first time the spectra of individual PAHs are exclusively used to fit the 5-15 μm region and analyze the spatial behavior of the aromatic infrared bands, providing fundamental, new information about astronomical PAH subpopulations including their dependence on, and response to, changes in local conditions.

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.

The 11.2 μm emission of PAHs in astrophysical objects

NASA Astrophysics Data System (ADS)

Candian, A.; Sarre, P. J.

2015-04-01

The 11.2-μm emission band belongs to the family of the `unidentified' infrared emission bands seen in many astronomical environments. In this work, we present a theoretical interpretation of the band characteristics and profile variation for a number of astrophysical sources in which the carriers are subject to a range of physical conditions. The results of Density Functional Theory calculations for the solo out-of-plane vibrational bending modes of large polycyclic aromatic hydrocarbon (PAH) molecules are used as input for a detailed emission model which includes the temperature and mass dependence of PAH band wavelength, and a PAH mass distribution that varies with object. Comparison of the model with astronomical spectra indicates that the 11.2-μm band asymmetry and profile variation can be explained principally in terms of the mass distribution of neutral PAHs with a small contribution from anharmonic effects.

Characteristics of PAHs from deep-frying and frying cooking fumes.

PubMed

Yao, Zhiliang; Li, Jing; Wu, Bobo; Hao, Xuewei; Yin, Yong; Jiang, Xi

2015-10-01

Cooking fumes are an important indoor source of polycyclic aromatic hydrocarbons (PAHs). Because indoor pollution has a more substantial impact on human health than outdoor pollution, PAHs from cooking fumes have drawn considerable attention. In this study, 16 PAHs emitted through deep-frying and frying methods using rapeseed, soybean, peanut, and olive oil were examined under a laboratory fume hood. Controlled experiments were conducted to collect gas- and particulate-phase PAHs emitted from the cooking oil fumes, and PAH concentrations were quantified via high-performance liquid chromatography (HPLC). The results show that deep-frying methods generate more PAHs and benzo[a]pyrene (B[a]P) (1.3 and 10.9 times, respectively) because they consume greater volumes of edible oil and involve higher oil temperatures relative to those of frying methods. In addition, the total B[a]Peq concentration of deep-frying is 2.2-fold larger than that of frying. Regarding the four types of edible oils studied, rapeseed oil produced more PAH emission than the other three oil varieties. For all of the cooking tests, three- and four-ringed PAHs were the main PAH components regardless of the food and oil used. Concerning the PAH partition between gas and particulate phase, the gaseous compounds accounted for 59-96 % of the total. Meanwhile, the particulate fraction was richer of high molecular weight PAHs (five-six rings). Deep-frying and frying were confirmed as important sources of PAH pollution in internal environments. The results of this study provide additional insights into the polluting features of PAHs produced via cooking activities in indoor environments.

Pulsed Discharge Nozzle Cavity Ring Down Spectroscopy of Cold PAH Ions

NASA Technical Reports Server (NTRS)

Biennier, Ludovic; Salama, Farid; Allamandola, Louis J.; Scherer, James J.; DeVincenzi, Donald (Technical Monitor)

2002-01-01

The gas-phase electronic absorption spectra of the naphthalene (C10H8(+)) and acenaphthene (C12H10(+)) cations have been measured in the visible range in a free 10 jet planar expansion in an attempt to collect data in an astrophysically relevant environment. The direct absorption spectra of two out of four bands measured of the gas-phase cold naphthalene cation along with the gas-phase vibronic absorption spectrum of the cold acenaphthene cation are reported for the first time. The study has been carried out using the ultrasensitive and versatile technique of cavity ringdown spectroscopy (CRDS) coupled to a pulsed discharge slit nozzle (PDN). The new CRDS-PDN set up is described and its characteristics are evaluated. The direct-absorption spectra of the PAH ions are discussed and compared to the gas-phase and solid-phase data available in the literature. The analysis of the results show that cold, free flying PAH ions are generated in the argon discharge primarily through soft Penning ionization. This enables the intrinsic band profiles to be measured, a key requirement for astrophysical applications.

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

Biodegradation of Mixed PAHs by PAH-Degrading Endophytic Bacteria.

PubMed

Zhu, Xuezhu; Ni, Xue; Waigi, Michael Gatheru; Liu, Juan; Sun, Kai; Gao, Yanzheng

2016-08-09

Endophytic bacteria can promote plant growth, induce plant defence mechanisms, and increase plant resistance to organic contaminants. The aims of the present study were to isolate highly PAH-degrading endophytic bacteria from plants growing at PAH-contaminated sites and to evaluate the capabilities of these bacteria to degrade polycyclic aromatic hydrocarbons (PAHs) in vitro, which will be beneficial for re-colonizing target plants and reducing plant PAH residues through the inoculation of plants with endophytic bacteria. Two endophytic bacterial strains P₁ (Stenotrophomonas sp.) and P₃ (Pseudomonas sp.), which degraded more than 90% of phenanthrene (PHE) within 7 days, were isolated from Conyza canadensis and Trifolium pretense L., respectively. Both strains could use naphthalene (NAP), PHE, fluorene (FLR), pyrene (PYR), and benzo(a)pyrene (B(a)P) as the sole sources of carbon and energy. Moreover, these bacteria reduced the contamination of mixed PAHs at high levels after inoculation for 7 days; strain P₁ degraded 98.0% NAP, 83.1% FLR, 87.8% PHE, 14.4% PYR, and 1.6% B(a)P, and strain P₃ degraded 95.3% NAP, 87.9% FLR, 90.4% PHE, 6.9% PYR, and negligible B(a)P. Notably, the biodegradation of PAHs could be promoted through additional carbon and nitrogen nutrients; therein, beef extract was suggested as the optimal co-substrate for the degradation of PAHs by these two strains (99.1% PHE was degraded within 7 days). Compared with strain P₁, strain P₃ has more potential for the use in the removal of PAHs from plant tissues. These results provide a novel perspective in the reduction of plant PAH residues in PAH-contaminated sites through inoculating plants with highly PAH-degrading endophytic bacteria.

Pore Water PAH Transport in Amended Sediment Caps

NASA Astrophysics Data System (ADS)

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

2009-05-01

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

THE NASA AMES PAH IR SPECTROSCOPIC DATABASE VERSION 2.00: UPDATED CONTENT, WEB SITE, AND ON(OFF)LINE TOOLS

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

Boersma, C.; Mattioda, A. L.; Allamandola, L. J.

A significantly updated version of the NASA Ames PAH IR Spectroscopic Database, the first major revision since its release in 2010, is presented. The current version, version 2.00, contains 700 computational and 75 experimental spectra compared, respectively, with 583 and 60 in the initial release. The spectra span the 2.5-4000 μm (4000-2.5 cm{sup -1}) range. New tools are available on the site that allow one to analyze spectra in the database and compare them with imported astronomical spectra as well as a suite of IDL object classes (a collection of programs utilizing IDL's object-oriented programming capabilities) that permit offline analysismore » called the AmesPAHdbIDLSuite. Most noteworthy among the additions are the extension of the computational spectroscopic database to include a number of significantly larger polycyclic aromatic hydrocarbons (PAHs), the ability to visualize the molecular atomic motions corresponding to each vibrational mode, and a new tool that allows one to perform a non-negative least-squares fit of an imported astronomical spectrum with PAH spectra in the computational database. Finally, a methodology is described in the Appendix, and implemented using the AmesPAHdbIDLSuite, that allows the user to enforce charge balance during the fitting procedure.« less

Extension of laboratory-measured soil spectra to field conditions

NASA Technical Reports Server (NTRS)

Stoner, E. R.; Baumgardner, M. F.; Weismiller, R. A.; Biehl, L. L.; Robinson, B. F.

1982-01-01

Spectral responses of two glaciated soils, Chalmers silty clay loam and Fincastle silt loam, formed under prairie grass and forest vegetation, respectively, were measured in the laboratory under controlled moisture equilibria using an Exotech Model 20C spectroradiometer to obtain spectral data in the laboratory under artificial illumination. The same spectroradiometer was used outdoors under solar illumination to obtain spectral response from dry and moistened field plots with and without corn residue cover, representing the two different soils. Results indicate that laboratory-measured spectra of moist soil are directly proportional to the spectral response of that same field-measured moist bare soil over the 0.52 micrometer to 1.75 micrometer wavelength range. The magnitudes of difference in spectral response between identically treated Chalmers and Fincastle soils are greatest in the 0.6 micrometers to 0.8 micrometer transition region between the visible and near infrared, regardless of field condition or laboratory preparation studied.

Primary sources and toxicity of PAHs in Milwaukee-area streambed sediment

USGS Publications Warehouse

Baldwin, Austin K.; Corsi, Steven R.; Lutz, Michelle A.; Ingersoll, Christopher G.; Dorman, Rebecca A.; Magruder, Christopher; Magruder, Matthew

2017-01-01

High concentrations of polycyclic aromatic hydrocarbons (PAHs) in streams can be a significant stressor to aquatic organisms. To understand the likely sources and toxicity of PAHs in Milwaukee-area streams, streambed sediment samples from 40 sites and parking lot dust samples from 6 sites were analyzed for 38 parent PAHs and 25 alkylated PAHs. Diagnostic ratios, profile correlations, principal components analysis, source-receptor modeling, and mass fractions analysis were used to identify potential PAH sources to streambed sediment samples, and land-use analysis was used to relate streambed sediment PAH concentrations to different urban-related land uses. On the basis of this multiple lines-of-evidence approach, coal-tar pavement sealant was indicated as the primary source of PAHs in a majority of streambed sediment samples, contributing an estimated 77% of total PAHs to samples, on average. Comparison to the Probable Effect Concentrations and (or) the Equilibrium Partitioning Sediment Benchmark indicates that 78% of stream sediment samples are likely to cause adverse effects to benthic organisms. Laboratory toxicity tests on a 16-sample subset of the streambed sites using the amphipod Hyalella azteca (28-day) and the midge Chironomus dilutus (10-day) measured significant reductions in one or more biological endpoints, including survival, in 75% of samples, with H. azteca more responsive than C. dilutus.

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.

Rotation-vibration interactions in the spectra of polycyclic aromatic hydrocarbons: Quinoline as a test-case species

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

Pirali, O.; Gruet, S.; Institut des Sciences Moléculaires d’Orsay, UMR8214 CNRS – Université Paris-Sud, Bât. 210, 91405 Orsay cedex

2015-03-14

Polycyclic aromatic hydrocarbons (PAHs) are highly relevant for astrophysics as possible, though controversial, carriers of the unidentified infrared emission bands that are observed in a number of different astronomical objects. In support of radio-astronomical observations, high resolution laboratory spectroscopy has already provided the rotational spectra in the vibrational ground state of several molecules of this type, although the rotational study of their dense infrared (IR) bands has only recently become possible using a limited number of experimental set-ups. To date, all of the rotationally resolved data have concerned unperturbed spectra. We presently report the results of a high resolution studymore » of the three lowest vibrational states of quinoline C{sub 9}H{sub 7}N, an N-bearing naphthalene derivative. While the pure rotational ground state spectrum of quinoline is unperturbed, severe complications appear in the spectra of the ν{sub 45} and ν{sub 44} vibrational modes (located at about 168 cm{sup −1} and 178 cm{sup −1}, respectively). In order to study these effects in detail, we employed three different and complementary experimental techniques: Fourier-transform microwave spectroscopy, millimeter-wave spectroscopy, and Fourier-transform far-infrared spectroscopy with a synchrotron radiation source. Due to the high density of states in the IR spectra of molecules as large as PAHs, perturbations in the rotational spectra of excited states should be ubiquitous. Our study identifies for the first time this effect and provides some insights into an appropriate treatment of such perturbations.« less

Developmant of a Reparametrized Semi-Empirical Force Field to Compute the Rovibrational Structure of Large PAHs

NASA Astrophysics Data System (ADS)

Fortenberry, Ryan

The Spitzer Space Telescope observation of spectra most likely attributable to diverse and abundant populations of polycyclic aromatic hydrocarbons (PAHs) in space has led to tremendous interest in these molecules as tracers of the physical conditions in different astrophysical regions. A major challenge in using PAHs as molecular tracers is the complexity of the spectral features in the 3-20 μm region. The large number and vibrational similarity of the putative PAHs responsible for these spectra necessitate determination for the most accurate basis spectra possible for comparison. It is essential that these spectra be established in order for the regions explored with the newest generation of observatories such as SOFIA and JWST to be understood. Current strategies to develop these spectra for individual PAHs involve either matrixisolation IR measurements or quantum chemical calculations of harmonic vibrational frequencies. These strategies have been employed to develop the successful PAH IR spectral database as a repository of basis functions used to fit astronomically observed spectra, but they are limited in important ways. Both techniques provide an adequate description of the molecules in their electronic, vibrational, and rotational ground state, but these conditions do not represent energetically hot regions for PAHs near strong radiation fields of stars and are not direct representations of the gas phase. Some non-negligible matrix effects are known in condensed-phase studies, and the inclusion of anharmonicity in quantum chemical calculations is essential to generate physically-relevant results especially for hot bands. While scaling factors in either case can be useful, they are agnostic to the system studied and are not robustly predictive. One strategy that has emerged to calculate the molecular vibrational structure uses vibrational perturbation theory along with a quartic force field (QFF) to account for higher-order derivatives of the potential

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.

Effects of different agricultural wastes on the dissipation of PAHs and the PAH-degrading genes in a PAH-contaminated soil.

PubMed

Han, Xuemei; Hu, Hangwei; Shi, Xiuzhen; Zhang, Limei; He, Jizheng

2017-04-01

Land application of agricultural wastes is considered as a promising bioremediation approach for cleaning up soils contaminated by aged polycyclic aromatic hydrocarbons (PAHs). However, it remains largely unknown about how microbial PAH-degraders, which play a key role in the biodegradation of soil PAHs, respond to the amendments of agricultural wastes. Here, a 90-day soil microcosm study was conducted to compare the effects of three agricultural wastes (i.e. WS, wheat stalk; MCSW, mushroom cultivation substrate waste; and CM, cow manure) on the dissipation of aged PAHs and the abundance and community structure of PAH-degrading microorganisms. The results showed that all the three agricultural wastes accelerated the dissipation of aged PAHs and significantly increased abundances of the bacterial 16S rRNA and PAH-degrading genes (i.e. pdo1 and nah). CM and MCSW with lower ratios of C:N eliminated soil PAHs more efficiently than WS with a high ratio of C:N. Low molecular weight PAHs were dissipated more quickly than those with high molecular weight. Phylogenetic analysis revealed that all of the nah and C12O clones were affiliated within Betaproteobacteria and Gammaproteobacteria, and application of agricultural wastes significantly changed the community structure of the microorganisms harboring nah and C12O genes, particularly in the CM treatment. Taken together, our findings suggest that the three tested agricultural wastes could accelerate the degradation of aged PAHs most likely through changing the abundances and community structure of microbial PAH degraders. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Predicting toxicity to Hyalella azteca in pyrogenic-impacted sediments-Do we need to analyze for all 34 PAHs?

PubMed

Geiger, Stephen C; Azzolina, Nicholas A; Nakles, David V; Hawthorne, Steven B

2016-07-01

Polycyclic aromatic hydrocarbons (PAHs) are major drivers of risk at many urban and/or industrialized sediment sites. The US Environmental Protection Agency (USEPA) currently recommends using measurements of 18 parent + 16 groups of alkylated PAHs (PAH-34) to assess the potential for sediment-bound PAHs to impact benthic organisms at these sites. ASTM Method D7363-13 was developed to directly measure low-level sediment porewater PAH concentrations. These concentrations are then compared to ambient water criteria (final chronic values [FCVs]) to assess the potential for impact to benthic organisms. The interlaboratory validation study that was used to finalize ASTM D7363-13 was developed using 24 of the 2-, 3-, and 4-ring PAHs (PAH-24) that are included in the USEPA PAH-34 analyte list. However, it is the responsibility of the user of ASTM Method D7363 to establish a test method to quantify the remaining 10 higher molecular weight PAHs that make up PAH-34. These higher molecular weight PAHs exhibit extremely low saturation solubilities that make their detection difficult in porewater, which has proven difficult to implement in a contract laboratory setting. As a result, commercial laboratories are hesitant to conduct the method on the entire PAH-34 analyte list. This article presents a statistical comparison of the ability of the PAH-24 and PAH-34 porewater results to predict survival of the freshwater amphipod Hyalella azteca, using the original 269 sediment samples used to gain ASTM D7363 Method approval. The statistical analysis shows that the PAH-24 are statistically indistinguishable from the PAH-34 for predicting toxicity. These results indicate that the analysis of freely dissolved porewater PAH-24 is sufficient for making risk-based decisions based on benthic invertebrate toxicity (survival and growth). This reduced target analyte list should result in a cost-saving for stakeholders and broader implementation of the method at PAH-impacted sediment sites

Fluorescence, Absorption, and Excitation Spectra of Polycyclic Aromatic Hydrocarbons as a Tool for Quantitative Analysis

ERIC Educational Resources Information Center

Rivera-Figueroa, A. M.; Ramazan, K. A.; Finlayson-Pitts, B. J.

2004-01-01

A quantitative and qualitative study of the interplay between absorption, fluorescence, and excitation spectra of pollutants called polycyclic aromatic hydrocarbons (PAHs) is conducted. The study of five PAH displays the correlation of the above-mentioned properties along with the associated molecular changes.

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.

IDEOS: Fitting Infrared Spectra from Dusty Galaxies

NASA Astrophysics Data System (ADS)

Viola, Vincent; Rupke, D.

2014-01-01

We fit models to heavily obscured infrared spectra taken by the Spitzer Space Telescope and prepare them for cataloguing in the Infrared Database of Extragalactic Observables from Spitzer (IDEOS). When completed, IDEOS will contain homogeneously measured mid-infrared spectroscopic observables of more than 4200 galaxies beyond the Local Group. The software we use, QUESTFit, models the spectra using up to three extincted blackbodies (including silicate, water ice, and hydrocarbon absorption) and PAH templates. We present results from a sample of the approximately 200 heavily obscured spectra that will be present in IDEOS.

Laboratory measurements of radiance and reflectance spectra of dilute primary-treated sewage sludge

NASA Technical Reports Server (NTRS)

Usry, J. W.; Witte, W. G.; Whitlock, C. H.; Gurganus, E. A.

1977-01-01

The feasibility of remotely monitoring ocean dumping of waste products such as acid and sewage sludge is evaluated. The laboratory arrangement, solar simulator, and test results from three experiments conducted in the laboratory are described. Radiance and reflectance spectra are presented for primary-treated sewage sludge mixed with two types of base water. Results indicate that upwelled reflectance varies in a near-linear manner with concentration and that the sludge has a practically flat signal response between 420 and 970 nm. Well-defined upwelled reflectance spectra were obtained for the sewage-sludge mixtures at all wavelengths and concentrations. The spectral-reflectance values appeared to be influenced by the type of base water, but this influence was small, especially for the mixtures with low concentrations of sewage sludge.

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

PubMed Central

2015-01-01

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

Composite of PAH-degrading endophytic bacteria reduces contamination and health risks caused by PAHs in vegetables.

PubMed

Wang, Jian; Liu, Juan; Ling, Wanting; Huang, Qingguo; Gao, Yanzheng

2017-11-15

Vegetables accumulate polycyclic aromatic hydrocarbons (PAHs) at high concentrations when grown in contaminated sites. Inoculation with PAH-degrading endophytic bacteria (EB PAH ) has been recognized as one of the most promising ways to remove PAHs from plant bodies; however, the performance of single endophytic bacteria is generally limited. This investigation used a composite of eight EB PAH to reduce the contamination and health risk posed by 16 EPA priority PAHs in vegetables including Chinese cabbage (Brassica chinensis L.) and pakchoi (Brassica campestris L.). Composite EB PAH have strong PAH degradation abilities, and more than 65% of ∑PAH were degraded after 10-day insuspension with composite EB PAH . Vegetable were contacted with composite EB PAH by seed soaking (SS) and leaf painting (LP) with an EB PAH cell incubation at OD 600nm =0.2-1.5. Compared with those in non-inoculated controls, the ∑PAH concentrations in edible parts of Chinese cabbage and pakchoi colonized by composite EB PAH via SS and LP with bacterial suspension at OD 600nm =0.2-1.5 were 42.07-70.77% and 15.79-53.20% lower, and the incremental lifetime cancer risk (ILCR) values for males and females were 31.78-84.08% and 26.60-83.40% smaller, respectively. SS was the optimal inoculation method for reducing PAH concentrations and ILCR values. Our results indicate that inoculating plants with composite EB PAH can lower the health risk posed by vegetables contaminated with PAHs, and may be used to mitigate plant PAH contamination. Copyright © 2017 Elsevier B.V. All rights reserved.

Microbial communities to mitigate contamination of PAHs in soil--possibilities and challenges: a review.

PubMed

Fernández-Luqueño, F; Valenzuela-Encinas, C; Marsch, R; Martínez-Suárez, C; Vázquez-Núñez, E; Dendooven, L

2011-01-01

Although highly diverse and specialized prokaryotic and eukaryotic microbial communities in soil degrade polycyclic aromatic hydrocarbons (PAHs), most of these are removed slowly. This review will discuss the biotechnological possibilities to increase the microbial dissipation of PAHs from soil as well as the main biological and biotechnological challenges. Microorganism provides effective and economically feasible solutions for soil cleanup and restoration. However, when the PAHs contamination is greater than the microbial ability to dissipate them, then applying genetically modified microorganisms might help to remove the contaminant. Nevertheless, it is necessary to have a more holistic review of the different individual reactions that are simultaneously taking place in a microbial cell and of the interactions microorganism-microorganism, microorganism-plant, microorganism-soil, and microorganisms-PAHs. Elucidating the function of genes from the PAHs-polluted soil and the study in pure cultures of isolated PAHs-degrading organisms as well as the generation of microorganisms in the laboratory that will accelerate the dissipation of PAHs and their safe application in situ have not been studied extensively. There is a latent environmental risk when genetically engineered microorganisms are used to remedy PAHs-contaminated soil.

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.

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

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.

Isolation of Adherent Polycyclic Aromatic Hydrocarbon (PAH)-Degrading Bacteria Using PAH-Sorbing Carriers

PubMed Central

Bastiaens, Leen; Springael, Dirk; Wattiau, Pierre; Harms, Hauke; deWachter, Rupert; Verachtert, Hubert; Diels, Ludo

2000-01-01

Two different procedures were compared to isolate polycyclic aromatic hydrocarbon (PAH)-utilizing bacteria from PAH-contaminated soil and sludge samples, i.e., (i) shaken enrichment cultures in liquid mineral medium in which PAHs were supplied as crystals and (ii) a new method in which PAH degraders were enriched on and recovered from hydrophobic membranes containing sorbed PAHs. Both techniques were successful, but selected from the same source different bacterial strains able to grow on PAHs as the sole source of carbon and energy. The liquid enrichment mainly selected for Sphingomonas spp., whereas the membrane method exclusively led to the selection of Mycobacterium spp. Furthermore, in separate membrane enrichment set-ups with different membrane types, three repetitive extragenic palindromic PCR-related Mycobacterium strains were recovered. The new Mycobacterium isolates were strongly hydrophobic and displayed the capacity to adhere strongly to different surfaces. One strain, Mycobacterium sp. LB501T, displayed an unusual combination of high adhesion efficiency and an extremely high negative charge. This strain may represent a new bacterial species as suggested by 16S rRNA gene sequence analysis. These results indicate that the provision of hydrophobic sorbents containing sorbed PAHs in the enrichment procedure discriminated in favor of certain bacterial characteristics. The new isolation method is appropriate to select for adherent PAH-degrading bacteria, which might be useful to biodegrade sorbed PAHs in soils and sludge. PMID:10788347

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.

PAHFIT: Properties of PAH Emission

NASA Astrophysics Data System (ADS)

Smith, J. D.; Draine, Bruce

2012-10-01

PAHFIT is an IDL tool for decomposing Spitzer IRS spectra of PAH emission sources, with a special emphasis on the careful recovery of ambiguous silicate absorption, and weak, blended dust emission features. PAHFIT is primarily designed for use with full 5-35 micron Spitzer low-resolution IRS spectra. PAHFIT is a flexible tool for fitting spectra, and you can add or disable features, compute combined flux bands, change fitting limits, etc., without changing the code. PAHFIT uses a simple, physically-motivated model, consisting of starlight, thermal dust continuum in a small number of fixed temperature bins, resolved dust features and feature blends, prominent emission lines (which themselves can be blended with dust features), as well as simple fully-mixed or screen dust extinction, dominated by the silicate absorption bands at 9.7 and 18 microns. Most model components are held fixed or are tightly constrained. PAHFIT uses Drude profiles to recover the full strength of dust emission features and blends, including the significant power in the wings of the broad emission profiles. This means the resulting feature strengths are larger (by factors of 2-4) than are recovered by methods which estimate the underlying continuum using line segments or spline curves fit through fiducial wavelength anchors.

Properties of polycyclic aromatic hydrocarbons in the northwest photon dominated region of NGC 7023. II. Traditional PAH analysis using k-means as a visualization tool

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

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

2014-11-10

Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer-IRS spectral map of the northwest photon dominated region (PDR) in NGC 7023 is analyzed using the 'traditional' approach in which the PAH bands and plateaus between 5.2-19.5 μm are isolated by subtracting the underlying continuum and removing H{sub 2} emission lines. The spectra are organized into seven spectroscopic bins by using k-means clustering. Each cluster corresponds to, and reveals, a morphological zone within NGC 7023. The zones self-organize parallel to the well-defined PDR front that coincides with an increase in intensity of the H{sub 2} emission lines. PAH band profiles and integratedmore » strengths are measured, classified, and mapped. The morphological zones revealed by the k-means clustering provides deeper insight into the conditions that drive variations in band strength ratios and evolution of the PAH population that otherwise would be lost. For example, certain band-band relations are bifurcated, revealing two limiting cases; one associated with the PDR, the other with the diffuse medium. Traditionally, PAH band strength ratios are used to gain insight into the properties of the emitting PAH population, i.e., charge, size, structure, and composition. Insights inferred from this work are compared and contrasted to those from Boersma et al. (first paper in this series), where the PAH emission in NGC 7023 is decomposed exclusively using the PAH spectra and tools made available through the NASA Ames PAH IR Spectroscopic Database.« less

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

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.

Isolation of adherent polycyclic aromatic hydrocarbon (PAH)-degrading bacteria using PAH-sorbing carriers

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

Bastiaens, L.; Springael, D.; Wattiau, P.

Two different procedures were compared to isolate polycyclic aromatic hydrocarbon (PAH)-utilizing bacteria from PAH-contaminated soil and sludge samples, i.e., (i) shaken enrichment cultures in liquid mineral medium in which PAHs were supplied as crystals and (ii) a new method in which PAH degraders were enriched on and recovered from hydrophobic membranes containing sorbed PAHs. Both techniques were successful, but selected from the same source different bacterial strains able to grow on PAHs as the sole source of carbon and energy. The liquid enrichment mainly selected for Sphingomonas spp., whereas the membrane method exclusively led to the selection of Mycobacterium spp.more » Furthermore, in separate membrane enrichment set-ups with different membrane types, three repetitive extragenic palindromic PCR-related Mycobacterium strains were recovered. The new Mycobactereium isolates were strongly hydrophobic and displayed the capacity to adhere strongly to different surfaces. One strain, Mycobacterium sp. LB501T, displayed an unusual combination of high adhesion efficiency and an extremely high negative charge. This strain may represent a new bacterial species as suggested by 16S rRNA gene sequence analysis. These results indicate that the provision of hydrophobic sorbents containing sorbed PAHs in the enrichment procedure discriminated in favor of certain bacterial characteristics. The new isolation method is appropriate to select for adherent PAH-degrading bacteria, which might be useful to biodegrade sorbed PAHs in soils and sludge.« less

Spectra Transfer Between a Fourier Transform Near-Infrared Laboratory and a Miniaturized Handheld Near-Infrared Spectrometer.

PubMed

Hoffmann, Uwe; Pfeifer, Frank; Hsuing, Chang; Siesler, Heinz W

2016-05-01

The aim of this contribution is to demonstrate the transfer of spectra that have been measured on two different laboratory Fourier transform near-infrared (FT-NIR) spectrometers to the format of a handheld instrument by measuring only a few samples with both spectrometer types. Thus, despite the extreme differences in spectral range and resolution, spectral data sets that have been collected and quantitative as well as qualitative calibrations that have been developed thereof, respectively, over a long period on a laboratory instrument can be conveniently transferred to the handheld system. Thus, the necessity to prepare completely new calibration samples and the effort required to develop calibration models when changing hardware platforms is minimized. The enabling procedure is based on piecewise direct standardization (PDS) and will be described for the data sets of a quantitative and a qualitative application case study. For this purpose the spectra measured on the FT-NIR laboratory spectrometers were used as "master" data and transferred to the "target" format of the handheld instrument. The quantitative test study refers to transmission spectra of three-component liquid solvent mixtures whereas the qualitative application example encompasses diffuse reflection spectra of six different current polymers. To prove the performance of the transfer procedure for quantitative applications, partial least squares (PLS-1) calibrations were developed for the individual components of the solvent mixtures with spectra transferred from the master to the target instrument and the cross-validation parameters were compared with the corresponding parameters obtained for spectra measured on the master and target instruments, respectively. To test the retention of the discrimination ability of the transferred polymer spectra sets principal component analyses (PCAs) were applied exemplarily for three of the six investigated polymers and their identification was demonstrated by

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.

Migration of polycyclic aromatic hydrocarbons (PAHs) in urban treatment sludge to the air during PAH removal applications.

PubMed

Karaca, Gizem; Cindoruk, S Siddik; Tasdemir, Yücel

2014-05-01

In the present study, the amounts of polycylic aromatic hydrocarbons (PAHs) penetrating into air during PAH removal applications from the urban treatment sludge were investigated. The effects of the temperature, photocatalyst type, and dose on the PAH removal efficiencies and PAH evaporation were explained. The sludge samples were taken from an urban wastewater treatment plant located in the city of Bursa, with 585,000 equivalent population. The ultraviolet C (UV-C) light of 254 nm wavelength was used within the UV applications performed on a specially designed setup. Internal air of the setup was vacuumed through polyurethane foam (PUF) columns in order to collect the evaporated PAHs from the sludge during the PAH removal applications. All experiments were performed with three repetitions. The PAH concentrations were measured by gas chromatography-mass spectrometry (GC-MS). It was observed that the amounts of PAHs penetrating into the air were increased with increase of temperature, and more than 80% of PAHs migrated to the air consisted of 3-ring compounds during the UV and UV-diethylamine (DEA) experiments at 38 and 53 degrees C. It was determined that 40% decrease was ensured in sigma12 (total of 12) PAH amounts with UV application and 13% of PAHs in sludge penetrated into the air. In the UV-TiO2 applications, a maximum 80% of sigma12 PAH removal was obtained by adding 0.5% TiO2 of dry weight of sludge. The quantity of PAH penetrating into air did not exceed 15%. UV-TiO2 applications ensured high levels of PAH removal in the sludge and also reduced the quantity of PAH penetrating into the air. Within the scope of the samples added with DEA, there was no increase in PAH removal efficiencies and the penetration of PAHs into air was not decreased. In light of these data, it was concluded that UV-TiO2 application is the most suitable PAH removal alternative that restricts the convection of PAH pollution.

Analyses of polycyclic aromatic hydrocarbon (PAH) and chiral-PAH analogues-methyl-β-cyclodextrin guest-host inclusion complexes by fluorescence spectrophotometry and multivariate regression analysis.

PubMed

Greene, LaVana; Elzey, Brianda; Franklin, Mariah; Fakayode, Sayo O

2017-03-05

The negative health impact of polycyclic aromatic hydrocarbons (PAHs) and differences in pharmacological activity of enantiomers of chiral molecules in humans highlights the need for analysis of PAHs and their chiral analogue molecules in humans. Herein, the first use of cyclodextrin guest-host inclusion complexation, fluorescence spectrophotometry, and chemometric approach to PAH (anthracene) and chiral-PAH analogue derivatives (1-(9-anthryl)-2,2,2-triflouroethanol (TFE)) analyses are reported. The binding constants (K b ), stoichiometry (n), and thermodynamic properties (Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS)) of anthracene and enantiomers of TFE-methyl-β-cyclodextrin (Me-β-CD) guest-host complexes were also determined. Chemometric partial-least-square (PLS) regression analysis of emission spectra data of Me-β-CD-guest-host inclusion complexes was used for the determination of anthracene and TFE enantiomer concentrations in Me-β-CD-guest-host inclusion complex samples. The values of calculated K b and negative ΔG suggest the thermodynamic favorability of anthracene-Me-β-CD and enantiomeric of TFE-Me-β-CD inclusion complexation reactions. However, anthracene-Me-β-CD and enantiomer TFE-Me-β-CD inclusion complexations showed notable differences in the binding affinity behaviors and thermodynamic properties. The PLS regression analysis resulted in square-correlation-coefficients of 0.997530 or better and a low LOD of 3.81×10 -7 M for anthracene and 3.48×10 -8 M for TFE enantiomers at physiological conditions. Most importantly, PLS regression accurately determined the anthracene and TFE enantiomer concentrations with an average low error of 2.31% for anthracene, 4.44% for R-TFE and 3.60% for S-TFE. The results of the study are highly significant because of its high sensitivity and accuracy for analysis of PAH and chiral PAH analogue derivatives without the need of an expensive chiral column, enantiomeric resolution, or use of a polarized

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.

Gaussian quadrature exponential sum modeling of near infrared methane laboratory spectra obtained at temperatures from 106 to 297 K

NASA Technical Reports Server (NTRS)

Giver, Lawrence P.; Benner, D. C.; Tomasko, M. G.; Fink, U.; Kerola, D.

1990-01-01

Transmission measurements made on near-infrared laboratory methane spectra have previously been fit using a Malkmus band model. The laboratory spectra were obtained in three groups at temperatures averaging 112, 188, and 295 K; band model fitting was done separately for each temperature group. These band model parameters cannot be used directly in scattering atmosphere model computations, so an exponential sum model is being developed which includes pressure and temperature fitting parameters. The goal is to obtain model parameters by least square fits at 10/cm intervals from 3800 to 9100/cm. These results will be useful in the interpretation of current planetary spectra and also NIMS spectra of Jupiter anticipated from the Galileo mission.

Theoretical Infrared Spectra for Polycyclic Aromatic Hydrocarbon Neutrals, Cations and Anions

NASA Technical Reports Server (NTRS)

Langhoff, Stephen R.

1995-01-01

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of the neutrals and cations of thirteen polycyclic aromatic hydrocarbons (PAHs) up to the size of ovalene. Calculations are also carried out for a few PAH anions. The DFT harmonic frequencies, when uniformly scaled by the factor of 0.958 to account primarily for anharmonicity, agree with the matrix isolation fundamentals to within an average error of about 10 per centimeter. Electron correlation is found to significantly reduce the intensities of many of the cation harmonics, bringing them into much better agreement with the available experimental data. While the theoretical infrared spectra agree well with the experimental data for the neutral systems and for many of the cations, there are notable discrepancies with the experimental matrix isolation data for some PAH cations that are difficult to explain in terms of limitations in the calculations. In agreement with previous theoretical work, the present calculations show that the relative intensities for the astronomical unidentified infrared (UIR) bands agree reasonably well with those for a distribution of polycyclic aromatic hydrocarbon (PAH) cations, but not with a distribution of PAH neutrals. We also observe that the infrared spectra of highly symmetrical cations such as coronene agree much better with astronomical observations than do those of, for example, the polyacenes such as tetracene and pentacene. The total integrated intensities for the neutral species are found to increase linearly with size, while the total integrated intensities are much larger for the cations and scale more nearly quadratically with size. We conclude that emission from moderate-sized highly symmetric PAH cations such as coronene and larger could account for the UIR bands.

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

PubMed

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

2015-01-01

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

Laboratory and Ambient Studies of the Products of Gas-Phase Hydroxyl and Nitrate Ion Radical-Initiated Reactions with Selected PAHs

NASA Astrophysics Data System (ADS)

Zimmermann, Kathryn Jean

Nitrated polycyclic aromatic hydrocarbon (nitro-PAH) product distributions from the gas-phase hydroxyl (OH) and nitrate (NO3) radical-initiated reactions with selected PAHs, as well as the heterogeneous reactions of surface-bound PAHs with N2O5 and HNO3, were investigated. Chapter 2 presents formation yields of nitro-PAHs from the gas-phase OH radical-initiated reactions of 1,7- and 2,7-dimethylnaphthalene (DMN) as a function of NO 2 concentration over the range 0.04-0.14 ppmv. The measured formation yields of dimethylnitronaphthalenes (DMNNs) under conditions that the OH-DMN adducts reacted solely with NO2 were 0.252 ± 0.094% for Σ1,7-DMNNs and 0.010 ± 0.005% for Σ2,7-DMNNs. 1,7-dimethyl-5-nitronaphthalene (1,7DM5NN) was the major nitro-isomer formed, with a limiting high-NO 2 concentration yield of 0.212 ± 0.080% and with equal reactions of the 1,7-DMN-OH adduct with NO2 and O2 occurring in air at 60 ± 39 ppbv of NO2, indicating that the OH-DMN adduct reaction with NO2 can be important at NO2 concentrations commonly found in urban atmospheres. Although the yields of the DMNNs are low, ≤0.3%, the DMNN (and ethylnitronaphthalene) profiles from chamber experiments match well with those observed in polluted urban areas under conditions where OH radical-initiated chemistry is dominant, such as Mexico City, Mexico. Chapter 3 examines the nitro-PAH products of gas-phase OH and NO 3 radicals and heterogeneous N2O5 reactions with fluoranthene, pyrene, benz[a]anthracene, chrysene, and triphenylene. Analysis of nitro-PAHs in the NIST diesel particulate SRM (1975) and selected ambient samples are also presented. 2-Nitrofluoranthene (2-NFL) was the most abundant nitro-PAH in Riverside, CA and Mexico City, and the mw 273 nitro-PAHs were observed in lower concentrations. However, in Tokyo, Japan, concentrations of 1- + 2-nitrotriphenylene (NTP) were more similar to those of 2-NFL. Comparing specific nitro-PAH ratios in ambient particulate samples from Tokyo, Mexico City

Low-density laboratory spectra near the He ii λ304 line

DOE PAGES

Träbert, Elmar; Beiersdorfer, Peter; Brickhouse, Nancy S.; ...

2016-02-02

Aims. Our aim is to interpret the EUV spectra of the solar corona, one hopes for laboratory data of specific chemical elements obtained under coronal conditions. Methods. EUV spectra of He, C, N, O, F, Ne, S, Ar, Fe, and Ni in a 40 Å wide wavelength interval near λ304 were excited in an electron beam ion trap. Results. We observe some two hundred lines about half of which are not yet identified and included in spectral models. Conclusions. Lastly, our data provide a check on the atomic data bases underlying the spectral models that are used to interpret solarmore » corona data. However, a multitude of mostly weak additional lines taken together represent a flux that is comparable to that of various primary lines.« less

Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons - Effect of ionization

NASA Technical Reports Server (NTRS)

De Frees, D. J.; Miller, M. D.; Talbi, D.; Pauzat, F.; Ellinger, Y.

1993-01-01

In order to test the hypothesis of ionized PAHs as possible carriers of the UIR bands, we realized a computational exploration on selected PAHs of small dimension in order to identify which changes ionization would induce on their IR spectra. In this study we performed ab initio calculations of the spectra of neutral and positively ionized naphthalene, anthracene, and pyrene. The results are significantly important. The frequencies in the cations are slightly shifted with respect to the neutral species, but no general conclusion can be reached from the three molecules considered. By contrast, the relative intensities of most vibrations are strongly affected by ionization, leading to a much better agreement between the calculated CH/CC vibration intensity ratios and those deduced from observations.

Removal Capacities of Polycyclic Aromatic Hydrocarbons (PAHs) by a Newly Isolated Strain from Oilfield Produced Water

PubMed Central

Qi, Yi-Bin; Wang, Chen-Yu; Lv, Cheng-Yuan; Lun, Zeng-Min; Zheng, Cheng-Gang

2017-01-01

The polycyclic aromatic hydrocarbon (PAH)-degrading strain Q8 was isolated from oilfield produced water. According to the analysis of a biochemical test, 16S rRNA gene, house-keeping genes and DNA–DNA hybridization, strain Q8 was assigned to a novel species of the genus Gordonia. The strain could not only grow in mineral salt medium (MM) and utilize naphthalene and pyrene as its sole carbon source, but also degraded mixed naphthalene, phenanthrene, anthracene and pyrene. The degradation ratio of these four PAHs reached 100%, 95.4%, 73.8% and 53.4% respectively after being degraded by Q8 for seven days. A comparative experiment found that the PAHs degradation efficiency of Q8 is higher than that of Gordonia alkaliphila and Gordonia paraffinivorans, which have the capacities to remove PAHs. Fourier transform infrared spectra, saturate, aromatic, resin and asphaltene (SARA) and gas chromatography–mass spectrometry (GC–MS) analysis of crude oil degraded by Q8 were also studied. The results showed that Q8 could utilize n-alkanes and PAHs in crude oil. The relative proportions of the naphthalene series, phenanthrene series, thiophene series, fluorene series, chrysene series, C21-triaromatic steroid, pyrene, and benz(a)pyrene were reduced after being degraded by Q8. Gordonia sp. nov. Q8 had the capacity to remediate water and soil environments contaminated by PAHs or crude oil, and provided a feasible way for the bioremediation of PAHs and oil pollution. PMID:28241412

BIODEGRADATION OF A PAH MIXTURE BY NATIVE SUBSURFACE MICROBIOTA. (R828770)

EPA Science Inventory

Laboratory microcosm studies were conducted to estimate biodegradation rates for a mixture of five polycyclic aromatic hydrocarbon compounds (PAHs). Static microcosms were assembled using soil samples from two locations collected at a No. 2 fuel oil-contaminated site in the At...

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

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.

Removal of Two High Molecular Weight PAHs from Soils with Different Water Content.

PubMed

Corona, Lilia; Dendooven, Luc; Chicken, Anaí; Hernández, Omar; Iturbe, Rosario

2017-11-01

Polycyclic aromatic hydrocarbons (PAHs) such as benz[a]anthracene (BA) and dibenz[a,h]anthracene (DBA), which are considered toxic, are frequently found in contaminated soils in Mexico. A laboratory-scale study monitored the degradation of the mixture of these two PAHs in three soils from different Mexican states (Tabasco, Morelos and Veracruz), each with different organic matter content, particle size distribution and incubated under different water content conditions. The hydrocarbons were extracted using microwave digestion and quantified by GC/MS. The removal of the PAHs, the growth of aerobic bacteria and microbial activity were determined in soil samples with and without a bacterial growth inhibitor (HgCl 2 ). The conclusion is that more than 90% of both contaminants was removed from the three soils, independently of the soil water content or the application of a bacterial growth inhibitor. Biological properties of the soils showed changes at the end of the experiment, but the results of the removal of PAHs were similar in the three soils.

Sonochemical degradation of PAH in aqueous solution. Part I: monocomponent PAH solution.

PubMed

David, Bernard

2009-02-01

The sonolysis of selected monocomponent PAH aqueous solution is studied at 20 and 506 kHz in the microg l(-1) range. The highest activity observed at 506 kHz, compared to 20 kHz, is tentatively explained by examination of the physical characteristics of bubbles (size and life-time) as well as by the calculation of the number of bubble at both frequency (5 x 10(3)bubbles l(-1) at 20 kHz and 4.5 x 10(9)bubbles l(-1) at 506 kHz). It is demonstrated that the main mechanism of sonodegradation is the pyrolysis of PAHs in the heart of the cavitation bubbles, and that a possible PAH oxidation by means of HO degrees appears as a minor way, since gaseous byproducts such as CO, CO2, C2H2 and CH4 have been detected. Correlations have been found by examination of kinetic variations in terms of the physical-chemical properties of PAHs. The rate constants of PAH degradation increase when the water solubility, the vapour pressure and the Henry's law constant increase.

Native oxy-PAHs, N-PACs, and PAHs in historically contaminated soils from Sweden, Belgium, and France: their soil-porewater partitioning behavior, bioaccumulation in Enchytraeus crypticus, and bioavailability.

PubMed

Arp, Hans Peter H; Lundstedt, Staffan; Josefsson, Sarah; Cornelissen, Gerard; Enell, Anja; Allard, Ann-Sofie; Kleja, Dan Berggren

2014-10-07

Soil quality standards are based on partitioning and toxicity data for laboratory-spiked reference soils, instead of real world, historically contaminated soils, which would be more representative. Here 21 diverse historically contaminated soils from Sweden, Belgium, and France were obtained, and the soil-porewater partitioning along with the bioaccumulation in exposed worms (Enchytraeus crypticus) of native polycyclic aromatic compounds (PACs) were quantified. The native PACs investigated were polycyclic aromatic hydrocarbons (PAHs) and, for the first time to be included in such a study, oxygenated-PAHs (oxy-PAHs) and nitrogen containing heterocyclic PACs (N-PACs). The passive sampler polyoxymethylene (POM) was used to measure the equilibrium freely dissolved porewater concentration, Cpw, of all PACs. The obtained organic carbon normalized partitioning coefficients, KTOC, show that sorption of these native PACs is much stronger than observed in laboratory-spiked soils (typically by factors 10 to 100), which has been reported previously for PAHs but here for the first time for oxy-PAHs and N-PACs. A recently developed KTOC model for historically contaminated sediments predicted the 597 unique, native KTOC values in this study within a factor 30 for 100% of the data and a factor 3 for 58% of the data, without calibration. This model assumes that TOC in pyrogenic-impacted areas sorbs similarly to coal tar, rather than octanol as typically assumed. Black carbon (BC) inclusive partitioning models exhibited substantially poorer performance. Regarding bioaccumulation, Cpw combined with liposome-water partition coefficients corresponded better with measured worm lipid concentrations, Clipid (within a factor 10 for 85% of all PACs and soils), than Cpw combined with octanol-water partition coefficients (within a factor 10 for 76% of all PACs and soils). E. crypticus mortality and reproducibility were also quantified. No enhanced mortality was observed in the 21 historically

Treatment Of Groundwater Contaminated With PAHs, Gasoline Hydrocarbons, And Methyl Tert-Butyl Ether In A Laboratory Biomass-Retaining Bioreactor

EPA Science Inventory

In this study, we investigated the treatability of co-mingled groundwater contaminated with polycyclic aromatic hydrocarbons (PAHs), gasoline hydrocarbons, and methyl tert-butyl ether (MtBE) using an ex-situ aerobic biotreatment system. The PAHs of interest were nap...

Influence of PAHs among other coastal environmental variables on total and PAH-degrading bacterial communities.

PubMed

Sauret, Caroline; Tedetti, Marc; Guigue, Catherine; Dumas, Chloé; Lami, Raphaël; Pujo-Pay, Mireille; Conan, Pascal; Goutx, Madeleine; Ghiglione, Jean-François

2016-03-01

We evaluated the relative impact of anthropogenic polycyclic aromatic hydrocarbons (PAHs) among biogeochemical variables on total, metabolically active, and PAH bacterial communities in summer and winter in surface microlayer (SML) and subsurface seawaters (SSW) across short transects along the NW Mediterranean coast from three harbors, one wastewater effluent, and one nearshore observatory reference site. At both seasons, significant correlations were found between dissolved total PAH concentrations and PAH-degrading bacteria that formed a gradient from the shore to nearshore waters. Accumulation of PAH degraders was particularly high in the SML, where PAHs accumulated. Harbors and wastewater outfalls influenced drastically and in a different way the total and active bacterial community structure, but they only impacted the communities from the nearshore zone (<2 km from the shore). By using direct multivariate statistical analysis, we confirmed the significant effect of PAH concentrations on the spatial and temporal dynamic of total and active communities in this area, but this effect was putted in perspective by the importance of other biogeochemical variables.

Mitigation of PAH and nitro-PAH emissions from nonroad diesel engines.

PubMed

Liu, Z Gerald; Wall, John C; Ottinger, Nathan A; McGuffin, Dana

2015-03-17

More stringent emission requirements for nonroad diesel engines introduced with U.S. Tier 4 Final and Euro Stage IV and V regulations have spurred the development of exhaust aftertreatment technologies. In this study, several aftertreatment configurations consisting of diesel oxidation catalysts (DOC), diesel particulate filters (DPF), Cu zeolite-, and vanadium-based selective catalytic reduction (SCR) catalysts, and ammonia oxidation (AMOX) catalysts are evaluated using both Nonroad Transient (NRTC) and Steady (8-mode NRSC) Cycles in order to understand both component and system-level effects of diesel aftertreatment on emissions of polycyclic aromatic hydrocarbons (PAH) and their nitrated derivatives (nitro-PAH). Emissions are reported for four configurations including engine-out, DOC+CuZ-SCR+AMOX, V-SCR+AMOX, and DOC+DPF+CuZ-SCR+AMOX. Mechanisms responsible for the reduction, and, in some cases, the formation of PAH and nitro-PAH compounds are discussed in detail, and suggestions are provided to minimize the formation of nitro-PAH compounds through aftertreatment design optimizations. Potency equivalency factors (PEFs) developed by the California Environmental Protection Agency are then applied to determine the impact of aftertreatment on PAH-derived exhaust toxicity. Finally, a comprehensive set of exhaust emissions including criteria pollutants, NO2, total hydrocarbons (THC), n-alkanes, branched alkanes, saturated cycloalkanes, aromatics, aldehydes, hopanes and steranes, and metals is provided, and the overall efficacy of the aftertreatment configurations is described. This detailed summary of emissions from a current nonroad diesel engine equipped with advanced aftertreatment can be used to more accurately model the impact of anthropogenic emissions on the atmosphere.

PAHs, NITRO-PAHs, HOPANES, AND STERANES IN LAKE TROUT FROM LAKE MICHIGAN

PubMed Central

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

2015-01-01

The present study examines concentrations and risks of polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), steranes, and hopanes in lake trout collected in Lake Michigan. A total of 74 fish were collected in 2 seasons at 3 offshore sites. The total PAH concentration (Σ9PAH) in whole fish ranged from 223 pg/g to 1704 pg/g wet weight, and PAH concentrations and profiles were similar across season, site, and sex. The total NPAH (Σ9NPAH) concentrations ranged from 0.2 pg/g to 31 pg/g wet weight, and carcinogenic compounds, including 1-nitropyrene and 6-nitrochrysene, were detected. In the fall, NPAH concentrations were low at the Illinois site (0.2–0.5 pg/g wet wt), and site profiles differed considerably; in the spring, concentrations and profiles were similar across sites, possibly reflecting changes in fish behavior. In the fall, the total sterane (Σ5Sterane) and total hopane (Σ2Hopane) levels reached 808 pg/g and 141 pg/g wet weight, respectively, but concentrations in the spring were 10 times lower. Concentrations in eggs (fall only) were on the same order of magnitude as those in whole fish. These results demonstrate the presence of target semivolatile organic compounds in a top predator fish, and are consistent with PAH biodilution observed previously. Using the available toxicity information for PAHs and NPAHs, the expected cancer risk from consumption of lake trout sampled are low. However, NPAHs contributed a significant portion of the toxic equivalencies in some samples. The present study provides the first measurements of NPAHs in freshwater fish, and results suggest that additional assessment is warranted. PMID:24764175

Modeling Soil Organic Carbon at Regional Scale by Combining Multi-Spectral Images with Laboratory Spectra.

PubMed

Peng, Yi; Xiong, Xiong; Adhikari, Kabindra; Knadel, Maria; Grunwald, Sabine; Greve, Mogens Humlekrog

2015-01-01

There is a great challenge in combining soil proximal spectra and remote sensing spectra to improve the accuracy of soil organic carbon (SOC) models. This is primarily because mixing of spectral data from different sources and technologies to improve soil models is still in its infancy. The first objective of this study was to integrate information of SOC derived from visible near-infrared reflectance (Vis-NIR) spectra in the laboratory with remote sensing (RS) images to improve predictions of topsoil SOC in the Skjern river catchment, Denmark. The second objective was to improve SOC prediction results by separately modeling uplands and wetlands. A total of 328 topsoil samples were collected and analyzed for SOC. Satellite Pour l'Observation de la Terre (SPOT5), Landsat Data Continuity Mission (Landsat 8) images, laboratory Vis-NIR and other ancillary environmental data including terrain parameters and soil maps were compiled to predict topsoil SOC using Cubist regression and Bayesian kriging. The results showed that the model developed from RS data, ancillary environmental data and laboratory spectral data yielded a lower root mean square error (RMSE) (2.8%) and higher R2 (0.59) than the model developed from only RS data and ancillary environmental data (RMSE: 3.6%, R2: 0.46). Plant-available water (PAW) was the most important predictor for all the models because of its close relationship with soil organic matter content. Moreover, vegetation indices, such as the Normalized Difference Vegetation Index (NDVI) and Enhanced Vegetation Index (EVI), were very important predictors in SOC spatial models. Furthermore, the 'upland model' was able to more accurately predict SOC compared with the 'upland & wetland model'. However, the separately calibrated 'upland and wetland model' did not improve the prediction accuracy for wetland sites, since it was not possible to adequately discriminate the vegetation in the RS summer images. We conclude that laboratory Vis

Modeling Soil Organic Carbon at Regional Scale by Combining Multi-Spectral Images with Laboratory Spectra

PubMed Central

Peng, Yi; Xiong, Xiong; Adhikari, Kabindra; Knadel, Maria; Grunwald, Sabine; Greve, Mogens Humlekrog

2015-01-01

There is a great challenge in combining soil proximal spectra and remote sensing spectra to improve the accuracy of soil organic carbon (SOC) models. This is primarily because mixing of spectral data from different sources and technologies to improve soil models is still in its infancy. The first objective of this study was to integrate information of SOC derived from visible near-infrared reflectance (Vis-NIR) spectra in the laboratory with remote sensing (RS) images to improve predictions of topsoil SOC in the Skjern river catchment, Denmark. The second objective was to improve SOC prediction results by separately modeling uplands and wetlands. A total of 328 topsoil samples were collected and analyzed for SOC. Satellite Pour l’Observation de la Terre (SPOT5), Landsat Data Continuity Mission (Landsat 8) images, laboratory Vis-NIR and other ancillary environmental data including terrain parameters and soil maps were compiled to predict topsoil SOC using Cubist regression and Bayesian kriging. The results showed that the model developed from RS data, ancillary environmental data and laboratory spectral data yielded a lower root mean square error (RMSE) (2.8%) and higher R2 (0.59) than the model developed from only RS data and ancillary environmental data (RMSE: 3.6%, R2: 0.46). Plant-available water (PAW) was the most important predictor for all the models because of its close relationship with soil organic matter content. Moreover, vegetation indices, such as the Normalized Difference Vegetation Index (NDVI) and Enhanced Vegetation Index (EVI), were very important predictors in SOC spatial models. Furthermore, the ‘upland model’ was able to more accurately predict SOC compared with the ‘upland & wetland model’. However, the separately calibrated ‘upland and wetland model’ did not improve the prediction accuracy for wetland sites, since it was not possible to adequately discriminate the vegetation in the RS summer images. We conclude that laboratory

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.

Prediction of the Ultraviolet-Visible Absorption Spectra of Polycyclic Aromatic Hydrocarbons (Dibenzo and Naphtho) Derivatives of Fluoranthene.

PubMed

Oña-Ruales, Jorge O; Ruiz-Morales, Yosadara

2017-06-01

The annellation theory method has been used to predict the locations of maximum absorbance (LMA) of the ultraviolet-visible (UV-Vis) spectral bands in the group of polycyclic aromatic hydrocarbons (PAHs) C 24 H 14 (dibenzo and naphtho) derivatives of fluoranthene (DBNFl). In this group of 21 PAHs, ten PAHs present a sextet migration pattern with four or more benzenoid rings that is potentially related to a high molecular reactivity and high mutagenic conduct. This is the first time that the locations of maximum absorbance in the UV-Vis spectra of naphth[1,2- a]aceanthrylene, dibenz[ a,l]aceanthrylene, indeno[1,2,3- de]naphthacene, naphtho[1,2- j]fluoranthene, naphth[2,1- e]acephenanthrylene, naphth[2,1- a]aceanthrylene, dibenz[ a,j]aceanthrylene, naphth[1,2- e]acephenanthrylene, and naphtho[2,1- j]fluoranthene have been predicted. Also, this represents the first report about the application of the annellation theory for the calculation of the locations of maximum absorbance in the UV-Vis spectra of PAHs with five-membered rings. Furthermore, this study constitutes the premier investigation beyond the pure benzenoid classical approach toward the establishment of a generalized annellation theory that will encompass not only homocyclic benzenoid and non-benzenoid PAHs, but also heterocyclic compounds.

[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.

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

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

Increased formation of carcinogenic PAH metabolites in fish promoted by nitrite.

PubMed

Shailaja, M S; Rajamanickam, Rani; Wahidulla, Solimabi

2006-09-01

Nitrite (NO(2)(-)), a highly reactive chemical species, accumulates in coastal waters as a result of pollution with nitrogenous waste and/or an imbalance in the bacterial processes of nitrification and denitrification. The present study probed the impact of nitrite (NO(2)(-)) on the metabolism of polycyclic aromatic hydrocarbons (PAHs) in fish. In a laboratory experiment, exposure of euryhaline fish, Oreochromis mossambicus to industrial effluents containing PAHs in the presence of NO(2)(-) enhanced the cytochrome P450-dependent biotransformation activity determined as 7-ethoxyresorufin-O-deethylase (EROD), by nearly 36% compared to the value observed in the absence of NO(2)(-) (50.2 +/- 6.74 pmol resorufin min(-1) g(-1) liver). Fixed wavelength fluorescence measurements in bile revealed maximum enhancement to have occurred in the metabolites of benzo[a]pyrene, a carcinogenic PAH. Lasting, sublethal physiological deterioration was apparent in fish exposed simultaneously to an oil refinery effluent and NO(2)(-), from the unremittingly decreasing liver somatic index, even after the withdrawal of the contaminants.

Distinguishing Vaccinium Species by Chemical Fingerprinting Based on NMR Spectra, Validated with Spectra Collected in Different Laboratories

PubMed Central

Markus, Michelle A.; Ferrier, Jonathan; Luchsinger, Sarah M.; Yuk, Jimmy; Cuerrier, Alain; Balick, Michael J.; Hicks, Joshua M.; Killday, K. Brian; Kirby, Christopher W.; Berrue, Fabrice; Kerr, Russell G.; Knagge, Kevin; Gödecke, Tanja; Ramirez, Benjamin E.; Lankin, David C.; Pauli, Guido F.; Burton, Ian; Karakach, Tobias K.; Arnason, John T.; Colson, Kimberly L.

2014-01-01

A method was developed to distinguish Vaccinium species based on leaf extracts using nuclear magnetic resonance spectroscopy. Reference spectra were measured on leaf extracts from several species, including lowbush blueberry (Vaccinium angustifolium), oval leaf huckleberry (Vaccinium ovalifolium), and cranberry (Vaccinium macrocarpon). Using principal component analysis, these leaf extracts were resolved in the scores plot. Analysis of variance statistical tests demonstrated that the three groups differ significantly on PC2, establishing that the three species can be distinguished by nuclear magnetic resonance. Soft independent modeling of class analogies models for each species also showed discrimination between species. To demonstrate the robustness of nuclear magnetic resonance spectroscopy for botanical identification, spectra of a sample of lowbush blueberry leaf extract were measured at five different sites, with different field strengths (600 versus 700 MHz), different probe types (cryogenic versus room temperature probes), different sample diameters (1.7 mm versus 5 mm), and different consoles (Avance I versus Avance III). Each laboratory independently demonstrated the linearity of their NMR measurements by acquiring a standard curve for chlorogenic acid (R2 = 0.9782 to 0.9998). Spectra acquired on different spectrometers at different sites classifed into the expected group for the Vaccinium spp., confirming the utility of the method to distinguish Vaccinium species and demonstrating nuclear magnetic resonance fingerprinting for material validation of a natural health product. PMID:24963620

Toxicokinetics of PAHs in Hexagenia

USGS Publications Warehouse

Stehly, Guy R.; Landrum, Peter F.; Henry, Mary G.; Klemm, C.

1990-01-01

The clearance of oxygen from water is inversely and linearly related to the weight of the mayfly nymphs, but oxygen clearances were always much less than the uptake clearances of the PAHs. The high PAH uptake clearance compared to oxygen clearance implies a greater surface area or efficiency for PAH accumulation from water.

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.

Destruction and survival of polycyclic aromatic hydrocarbons in active galaxies

NASA Technical Reports Server (NTRS)

Voit, G. M.

1992-01-01

Infrared spectra of dusty galactic environments often contain emission features attributed to polycyclic aromatic hydrocarbons or PAHs, which can be considered to be very small grains or very large molecules. Although IR spectra of starburst galaxies almost always show these emission features, similar spectra of active galaxies are usually featureless. Even in those active galaxies that do exhibit PAH emission, the PAHs still appear to be eradicated from the nuclear region. This dichotomy suggests that PAHs are destroyed by the intense hard radiation field from an AGN. Laboratory experiments show that certain PAHs are, in fact, so effectively destroyed by individual EUV and X-ray photons that they cannot survive even at kiloparsec distances from active nuclei. Regions within active galaxies that do show PAH emission must therefore be shielded from the central X-ray source by a substantial column density of X-ray absorbing gas.

On-line and in-situ detection of polycyclic aromatic hydrocarbons (PAH) on aerosols via thermodesorption and laser-induced fluorescence spectroscopy.

PubMed

Panne, U; Knöller, A; Kotzick, R; Niessner, R

2000-02-01

A fiber optical sensor system for the determination of polycyclic aromatic hydrocarbons (PAH) on aerosols by laser-induced, time-resolved fluorescence is combined with a thermodesorption device. The sensor system is based on an aerosol flow cell, which is fibre-optically coupled to a pulsed nitrogen laser for excitation and the detection system. Time-resolved fluorescence emission spectra are detected by a monochromator equipped with a photomultiplier and a fast digital storage oscilloscope. The analytical figures of merit of the thermodenuder are reported for benzo[a]pyrene, benzo[b]fluoranthene, and benzo[ghi]-perylene on ultrafine soot and NaCl aerosols. By thermodesorption of the PAH, problems due to quenching of the PAH fluorescence by the bulk aerosol material or excimer formation on the aerosol surface were avoided. For the PAH under study, the sensitivity was improved considerably and detection limits between 110 and 850 ng m(-3) were attained, while a response time of 2-3 min was achieved with the thermodenuder. A calibration for PAH on ultrafine soot and NaCl aerosols was established independent of the aerosol substrate.

Astrochemistry: Recent Advances in the Study of Carbon Molecules in Space

NASA Technical Reports Server (NTRS)

Salama, Farid

2006-01-01

Carbon molecules and ions play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are the best-known candidates to account for the infrared emission bands (UIR bands) and PAH spectral features are now being used as probes of the interstellar medium in Galactic and extra-galactic environments. 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 exist in the emission and absorption interstellar zones. An extensive laboratory program has been developed in various laboratories to characterize the physical and chemical properties of PAHs in astrophysical environments and to describe how they influence the radiation and energy balance in space and the interstellar chemistry. In particular, laboratory experiments provide measurements of the spectral characteristics of interstellar PAH analogs from the ultraviolet and visible range to the infrared range for comparison with astronomical data. The harsh physical conditions of the interstellar medium - characterized by a low temperature, an absence of collisions and strong ultraviolet radiation fields - are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions are formed from the neutral precursors in an isolated environment at low temperature (of the order of 100 K). The spectra of neutral and ionized PAHs are measured using the high sensitivity methods of cavity ring down spectroscopy (CRDS). These experiments provide unique information on the spectra of free, cold large carbon

Aerobic Bioremediation of PAH Contaminated Soil Results in Increased Genotoxicity and Developmental Toxicity.

PubMed

Chibwe, Leah; Geier, Mitra C; Nakamura, Jun; Tanguay, Robert L; Aitken, Michael D; Simonich, Staci L Massey

2015-12-01

The formation of more polar and toxic polycyclic aromatic hydrocarbon (PAH) transformation products is one of the concerns associated with the bioremediation of PAH-contaminated soils. Soil contaminated with coal tar (prebioremediation) from a former manufactured gas plant (MGP) site was treated in a laboratory scale bioreactor (postbioremediation) and extracted using pressurized liquid extraction. The soil extracts were fractionated, based on polarity, and analyzed for 88 PAHs (unsubstituted, oxygenated, nitrated, and heterocyclic PAHs). The PAH concentrations in the soil tested, postbioremediation, were lower than their regulatory maximum allowable concentrations (MACs), with the exception of the higher molecular weight PAHs (BaA, BkF, BbF, BaP, and IcdP), most of which did not undergo significant biodegradation. The soil extract fractions were tested for genotoxicity using the DT40 chicken lymphocyte bioassay and developmental toxicity using the embryonic zebrafish (Danio rerio) bioassay. A statistically significant increase in genotoxicity was measured in the unfractionated soil extract, as well as in four polar soil extract fractions, postbioremediation (p < 0.05). In addition, a statistically significant increase in developmental toxicity was measured in one polar soil extract fraction, postbioremediation (p < 0.05). A series of morphological abnormalities, including peculiar caudal fin malformations and hyperpigmentation in the tail, were measured in several soil extract fractions in embryonic zebrafish, both pre- and postbioremediation. The increased toxicity measured postbioremediation is not likely due to the 88 PAHs measured in this study (including quinones), because most were not present in the toxic polar fractions and/or because their concentrations did not increase postbioremediation. However, the increased toxicity measured postbioremediation is likely due to hydroxylated and carboxylated transformation products of the 3- and 4-ring PAHs (PHE, 1

Aerobic Bioremediation of PAH Contaminated Soil Results in Increased Genotoxicity and Developmental Toxicity

PubMed Central

Chibwe, Leah; Geier, Mitra C.; Nakamura, Jun; Tanguay, Robert L.; Aitken, Michael D.; Simonich, Staci L. Massey

2015-01-01

The formation of more polar and toxic polycyclic aromatic hydrocarbon (PAH) transformation products is one of the concerns associated with the bioremediation of PAH-contaminated soils. Soil contaminated with coal tar (pre-bioremediation) from a former manufactured gas plant (MGP) site was treated in a laboratory scale bioreactor (post-bioremediation) and extracted using pressurized liquid extraction. The soil extracts were fractionated, based on polarity, and analyzed for 88 PAHs (unsubstituted, oxygenated, nitrated, and heterocyclic PAHs). The PAH concentrations in the soil tested, post-bioremediation, were lower than their regulatory maximum allowable concentrations (MACs), with the exception of the higher molecular weight PAHs (BaA, BkF, BbF, BaP, and IcdP), most of which did not undergo significant biodegradation. The soil extract fractions were tested for genotoxicity using the DT40 chicken lymphocyte bioassay and developmental to xicity using the embryonic zebrafish (Danio rerio) bioassay. A statistically significant increase in genotoxicity was measured in the unfractionated soil extract, as well as in four polar soil extract fractions, post-bioremediation (p < 0.05). In addition, a statistically significant increase in developmental toxicity was measured in one polar soil extract fraction, post-bioremediation (p < 0.05). A series of morphological abnormalities, including peculiar caudal fin malformations and hyperpigmentation in the tail, were measured in several soil extract fractions in embryonic zebrafish, both pre- and post-bioremediation. The increased toxicity measured post-bioremediation is not likely due to the 88 PAHs measured in this study (including quinones), because most were not present in the toxic polar fractions and/or because their concentrations did not increase post-bioremediation. However, the increased toxicity measured post-bioremediation is likely due to hydroxylated and carboxylated transformation products of the 3- and 4-ring PAHs

Distribution of polycyclic aromatic hydrocarbons (PAHs) in rivers and estuaries in Malaysia: a widespread input of petrogenic PAHs.

PubMed

Zakaria, Mohamad Pauzi; Takada, Hideshige; Tsutsumi, Shinobu; Ohno, Kei; Yamada, Junya; Kouno, Eriko; Kumata, Hidetoshi

2002-05-01

This is the first publication on the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in riverine and coastal sediments in South East Asia where the rapid transfer of land-based pollutants into aquatic environments by heavy rainfall and runoff waters is of great concern. Twenty-nine Malaysian riverine and coastal sediments were analyzed for PAHs (3-7 rings) by gas chromatography mass spectrometry. Total PAHs concentrations in the sediment ranged from 4 to 924 ng/g. Alkylated homologues were abundant for all sediment samples. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P), an index of petrogenic PAHs contribution, was more than unity for 26 sediment samples and more than 3 for seven samples for urban rivers covering a broad range of locations. The MP/P ratio showed a strong correlation with the total PAHs concentrations, with an r2 value of 0.74. This ratio and all other compositional features indicated that Malaysian urban sediments are heavily impacted by petrogenic PAHs. This finding is in contrast to other studies reported in many industrialized countries where PAHs are mostly of pyrogenic origin. The MP/P ratio was also significantly correlated with higher molecular weight PAHs such as benzo[a]pyrene, suggesting unique PAHs source in Malaysia which contains both petrogenic PAHs and pyrogenic PAHs. PAHs and hopanes fingerprints indicated that used crankcase oil is one of the major contributors of the sedimentary PAHs. Two major routes of inputs to aquatic environments have been identified: (1) spillage and dumping of waste crankcase oil and (2) leakage of crankcase oils from vehicles onto road surfaces, with the subsequent washout by street runoff. N-Cyclohexyl-2-benzothiazolamine (NCBA), a molecular marker of street dust, was detected in the polluted sediments. NCBA and other biomarker profiles confirmed our hypothesis of the input from street dust contained the leaked crankcase oil. The fingerprints excluded crude oil

Triolein embedded cellulose acetate membrane as a tool to evaluate sequestration of PAHs in lake sediment core at large temporal scale.

PubMed

Tao, Yuqiang; Xue, Bin; Yao, Shuchun; Deng, Jiancai; Gui, Zhifan

2012-04-03

Although numerous studies have addressed sequestration of hydrophobic organic compounds (HOCs) in laboratory, little attention has been paid to its evaluation method in field at large temporal scale. A biomimetic tool, triolein embedded cellulose acetate membrane (TECAM), was therefore tested to evaluate sequestration of six PAHs with various hydrophobicity in a well-dated sediment core sampled from Nanyi Lake, China. Properties of sediment organic matter (OM) varying with aging time dominated the sequestration of PAHs in the sediment core. TECAM-sediment accumulation factors (MSAFs) of the PAHs declined with aging time, and significantly correlated with the corresponding biota-sediment accumulation factors (BSAFs) for gastropod (Bellamya aeruginosa) simultaneously incubated in the same sediment slices. Sequestration rates of the PAHs in the sediment core evaluated by TECAM were much lower than those obtained from laboratory study. The relationship between relative availability for TECAM (MSAF(t)/MSAF(0)) and aging time followed the first order exponential decay model. MSAF(t)/MSAF(0) was well-related to the minor changes of the properties of OM varying with aging time. Compared with chemical extraction, sequestration reflected by TECAM was much closer to that by B. aeruginosa. In contrast to B. aeruginosa, TECAM could avoid metabolism and the influences from feeding and other behaviors of organisms, and it is much easier to deploy and ready in laboratory. Hence TECAM provides an effective and convenient way to study sequestration of PAHs and probably other HOCs in field at large temporal scale.

Polycyclic Aromatic Hydrocarbon (PAH) and Oxygenated PAH (OPAH) Air–Water Exchange during the Deepwater Horizon Oil Spill

PubMed Central

2015-01-01

Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during, and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water–air boundary was determined. This is the first report of vapor phase and flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 1 and 24 ng/m3 and 0.3 and 27 ng/m3, respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air–water flux of 13 individual PAHs were strongly associated with the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi in the summer, each nominally 10 000 ng/m2/day. Acenaphthene was the PAH with the highest observed volatilization rate of 6800 ng/m2/day in September 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air–water chemical flux determinations with passive sampling technology. PMID:25412353

Polycyclic aromatic hydrocarbon (PAH) and oxygenated PAH (OPAH) air-water exchange during the deepwater horizon oil spill.

PubMed

Tidwell, Lane G; Allan, Sarah E; O'Connell, Steven G; Hobbie, Kevin A; Smith, Brian W; Anderson, Kim A

2015-01-06

Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during, and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water-air boundary was determined. This is the first report of vapor phase and flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 1 and 24 ng/m(3) and 0.3 and 27 ng/m(3), respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air-water flux of 13 individual PAHs were strongly associated with the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi in the summer, each nominally 10,000 ng/m(2)/day. Acenaphthene was the PAH with the highest observed volatilization rate of 6800 ng/m(2)/day in September 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air-water chemical flux determinations with passive sampling technology.

Distinguishing Vaccinium species by chemical fingerprinting based on NMR spectra, validated with spectra collected in different laboratories.

PubMed

Markus, Michelle A; Ferrier, Jonathan; Luchsinger, Sarah M; Yuk, Jimmy; Cuerrier, Alain; Balick, Michael J; Hicks, Joshua M; Killday, K Brian; Kirby, Christopher W; Berrue, Fabrice; Kerr, Russell G; Knagge, Kevin; Gödecke, Tanja; Ramirez, Benjamin E; Lankin, David C; Pauli, Guido F; Burton, Ian; Karakach, Tobias K; Arnason, John T; Colson, Kimberly L

2014-06-01

A method was developed to distinguish Vaccinium species based on leaf extracts using nuclear magnetic resonance spectroscopy. Reference spectra were measured on leaf extracts from several species, including lowbush blueberry (Vaccinium angustifolium), oval leaf huckleberry (Vaccinium ovalifolium), and cranberry (Vaccinium macrocarpon). Using principal component analysis, these leaf extracts were resolved in the scores plot. Analysis of variance statistical tests demonstrated that the three groups differ significantly on PC2, establishing that the three species can be distinguished by nuclear magnetic resonance. Soft independent modeling of class analogies models for each species also showed discrimination between species. To demonstrate the robustness of nuclear magnetic resonance spectroscopy for botanical identification, spectra of a sample of lowbush blueberry leaf extract were measured at five different sites, with different field strengths (600 versus 700 MHz), different probe types (cryogenic versus room temperature probes), different sample diameters (1.7 mm versus 5 mm), and different consoles (Avance I versus Avance III). Each laboratory independently demonstrated the linearity of their NMR measurements by acquiring a standard curve for chlorogenic acid (R(2) = 0.9782 to 0.9998). Spectra acquired on different spectrometers at different sites classifed into the expected group for the Vaccinium spp., confirming the utility of the method to distinguish Vaccinium species and demonstrating nuclear magnetic resonance fingerprinting for material validation of a natural health product. Georg Thieme Verlag KG Stuttgart · New York.

Occupational PAH exposures during prescribed pile burns.

PubMed

Robinson, M S; Anthony, T R; Littau, S R; Herckes, P; Nelson, X; Poplin, G S; Burgess, J L

2008-08-01

Wildland firefighters are exposed to particulate matter and gases containing polycyclic aromatic hydrocarbons (PAHs), many of which are known carcinogens. Our objective was to evaluate the extent of firefighter exposure to particulate and PAHs during prescribed pile burns of mainly ponderosa pine slash and determine whether these exposures were correlated with changes in urinary 1-hydroxypyrene (1-HP), a PAH metabolite. Personal and area sampling for particulate and PAH exposures were conducted on the White Mountain Apache Tribe reservation, working with 21 Bureau of Indian Affairs/Fort Apache Agency wildland firefighters during the fall of 2006. Urine samples were collected pre- and post-exposure and pulmonary function was measured. Personal PAH exposures were detectable for only 3 of 16 PAHs analyzed: naphthalene, phenanthrene, and fluorene, all of which were identified only in vapor-phase samples. Condensed-phase PAHs were detected in PM2.5 area samples (20 of 21 PAHs analyzed were detected, all but naphthalene) at concentrations below 1 microg m(-3). The total PAH/PM2.5 mass fractions were roughly a factor of two higher during smoldering (1.06 +/- 0.15) than ignition (0.55 +/- 0.04 microg mg(-1)). There were no significant changes in urinary 1-HP or pulmonary function following exposure to pile burning. In summary, PAH exposures were low in pile burns, and urinary testing for a PAH metabolite failed to show a significant difference between baseline and post-exposure measurements.

Occupational PAH Exposures during Prescribed Pile Burns

PubMed Central

Robinson, M. S.; Anthony, T. R.; Littau, S. R.; Herckes, P.; Nelson, X.; Poplin, G. S.; Burgess, J. L.

2008-01-01

Wildland firefighters are exposed to particulate matter and gases containing polycyclic aromatic hydrocarbons (PAHs), many of which are known carcinogens. Our objective was to evaluate the extent of firefighter exposure to particulate and PAHs during prescribed pile burns of mainly ponderosa pine slash and determine whether these exposures were correlated with changes in urinary 1-hydroxypyrene (1-HP), a PAH metabolite. Personal and area sampling for particulate and PAH exposures were conducted on the White Mountain Apache Tribe reservation, working with 21 Bureau of Indian Affairs/Fort Apache Agency wildland firefighters during the fall of 2006. Urine samples were collected pre- and post-exposure and pulmonary function was measured. Personal PAH exposures were detectable for only 3 of 16 PAHs analyzed: naphthalene, phenanthrene, and fluorene, all of which were identified only in vapor-phase samples. Condensed-phase PAHs were detected in PM2.5 area samples (20 of 21 PAHs analyzed were detected, all but naphthalene) at concentrations below 1 μg m−3. The total PAH/PM2.5 mass fractions were roughly a factor of two higher during smoldering (1.06 ± 0.15) than ignition (0.55 ± 0.04 μg mg−1). There were no significant changes in urinary 1-HP or pulmonary function following exposure to pile burning. In summary, PAH exposures were low in pile burns, and urinary testing for a PAH metabolite failed to show a significant difference between baseline and post-exposure measurements. PMID:18515848

PROPERTIES OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE NORTHWEST PHOTON DOMINATED REGION OF NGC 7023. III. QUANTIFYING THE TRADITIONAL PROXY FOR PAH CHARGE AND ASSESSING ITS ROLE

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

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

2015-06-10

Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer/IRS spectral map of the northwest photon dominated region (PDR) in NGC 7023 is analyzed. Here, results from fitting the 5.2–14.5 μm spectrum at each pixel using exclusively PAH spectra from the NASA Ames PAH IR Spectroscopic Database (www.astrochem.org/pahdb/) and observed PAH band strength ratios, determined after isolating the PAH bands, are combined. This enables the first quantitative and spectrally consistent calibration of PAH charge proxies. Calibration is straightforward because the 6.2/11.2 μm PAH band strength ratio varies linearly with the ionized fraction (PAH ionization parameter) as determined from the intrinsic properties ofmore » the individual PAHs comprising the database. This, in turn, can be related to the local radiation field, electron density, and temperature. From these relations diagnostic templates are developed to deduce the PAH ionization fraction and astronomical environment in other objects. The commonly used 7.7/11.2 μm PAH band strength ratio fails as a charge proxy over a significant fraction of the nebula. The 11.2/12.7 μm PAH band strength ratio, commonly used as a PAH erosion indicator, is revealed to be a better tracer for PAH charge across NGC 7023. Attempting to calibrate the 12.7/11.2 μm PAH band strength ratio against the PAH hydrogen adjacency ratio (duo+trio)/solo is, unexpectedly, anti-correlated. This work both validates and extends the results from Paper I and Paper II.« less

Properties of Polycyclic Aromatic Hydrocarbons in the Northwest Photon Dominated Region of NGC 7023. III. Quantifying the Traditional Proxy for PAH Charge and Assessing its Role

NASA Astrophysics Data System (ADS)

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

2015-06-01

Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer/IRS spectral map of the northwest photon dominated region (PDR) in NGC 7023 is analyzed. Here, results from fitting the 5.2-14.5 μm spectrum at each pixel using exclusively PAH spectra from the NASA Ames PAH IR Spectroscopic Database (www.astrochem.org/pahdb/) and observed PAH band strength ratios, determined after isolating the PAH bands, are combined. This enables the first quantitative and spectrally consistent calibration of PAH charge proxies. Calibration is straightforward because the 6.2/11.2 μm PAH band strength ratio varies linearly with the ionized fraction (PAH ionization parameter) as determined from the intrinsic properties of the individual PAHs comprising the database. This, in turn, can be related to the local radiation field, electron density, and temperature. From these relations diagnostic templates are developed to deduce the PAH ionization fraction and astronomical environment in other objects. The commonly used 7.7/11.2 μm PAH band strength ratio fails as a charge proxy over a significant fraction of the nebula. The 11.2/12.7 μm PAH band strength ratio, commonly used as a PAH erosion indicator, is revealed to be a better tracer for PAH charge across NGC 7023. Attempting to calibrate the 12.7/11.2 μm PAH band strength ratio against the PAH hydrogen adjacency ratio (duo+trio)/solo is, unexpectedly, anti-correlated. This work both validates and extends the results from Paper I and Paper II.

Parking lot sealcoat: a major source of polycyclic aromatic hydrocarbons (PAHs) in urban and suburban environments

USGS Publications Warehouse

Van Metre, Peter C.; Mahler, Barbara J.; Scoggins, Mateo; Hamilton, Pixie A.

2005-01-01

Collaborative studies by the City of Austin and the U. S. Geological Survey (USGS) have identified coal-tar based sealcoat—the black, shiny emulsion painted or sprayed on asphalt pavement such as parking lots—as a major and previously unrecognized source of polycyclic aromatic hydrocarbon (PAH) contamination. Several PAHs are suspected human carcinogens and are toxic to aquatic life. Studies in Austin, Texas, showed that particles in runoff from coal-tar based sealcoated parking lots had concentrations of PAHs that were about 65 times higher than concentrations in particles washed off parking lots that had not been sealcoated. Biological studies, conducted by the City of Austin in the field and in the laboratory, indicated that PAH levels in sediment contaminated with abraded sealcoat were toxic to aquatic life and were degrading aquatic communities, as indicated by loss of species and decreased numbers of organisms. Identification of this source of PAHs may help to improve future strategies for controlling these compounds in urban water bodies across the Nation where parking lot sealcoat is used.

Laboratory absorption spectra of molecules at interstellar cloud temperatures - First measurements on CO at about 97 nm

NASA Technical Reports Server (NTRS)

Smith, P. L.; Yoshino, K.; Stark, G.; Ito, K.; Stevens, M. H.

1991-01-01

In the 91-100 nm spectral region, where absorption of photons by interstellar CO usually leads to dissociation, laboratory spectra obtained at 295 K show that most CO bands are both overlapped and perturbed. Reliable band oscillator strengths cannot be extracted from such spectra. As a consequence, synthetic extreme-ultraviolet absorption spectra for CO at the low temperatures that prevail in interstellar clouds are uncertain. A supersonic expansion technique has been used to cool CO to 30 K and three bands in the 97-nm region have been studied with high spectral resolution. The measured spectrum at 30 K is in reasonable agreement with some published modeled spectra, but the ratios of integrated cross sections are somewhat different from those determined from low resolution spectra obtained at 295 K, in which the bands are blended.

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.

BIODEGRADATION OF A PAH MIXTURE BY NATIVE SUBSURFACE MICROBIOTA. (R828770C004)

EPA Science Inventory

Laboratory microcosm studies were conducted to estimate biodegradation rates for a mixture of five polycyclic aromatic hydrocarbon compounds (PAHs). Static microcosms were assembled using soil samples from two locations collected at a No. 2 fuel oil-contaminated site in the At...

Pavement Sealcoat, PAHs, and the Environment

NASA Astrophysics Data System (ADS)

Van Metre, P. C.; Mahler, B. J.

2011-12-01

Recent research by the USGS has identified coal-tar-based pavement sealants as a major source of polycyclic aromatic hydrocarbons (PAHs) to the environment. Coal-tar-based sealcoat is commonly used to coat parking lots and driveways and is typically is 20-35 percent coal tar pitch, a known human carcinogen. Several PAHs are suspected mutagens, carcinogens, and (or) teratogens. In the central and eastern U.S. where the coal-tar-based sealants dominate use, sum-PAH concentration in dust particles from sealcoated pavement is about 1,000 times higher than in the western U.S. where the asphalt-based formulation is prevalent. Source apportionment modeling indicates that particles from sealcoated pavement are contributing the majority of the PAHs to recent lake sediment in 35 U.S. urban lakes and are the primary cause of upward trends in PAHs in many of these lakes. Mobile particles from parking lots with coal-tar-based sealcoat are tracked indoors, resulting in elevated PAH concentrations in house dust. In a recently completed study, volatilization fluxes of PAHs from sealcoated pavement were estimated to be about 60 times fluxes from unsealed pavement. Using a wide variety of methods, the author and colleagues have shown that coal-tar-based sealcoat is a major source of PAHs to the urban environment and might pose risks to aquatic life and human health.

Quantification of PAHs and oxy-PAHs on airborne particulate matter in Chiang Mai, Thailand, using gas chromatography high resolution mass spectrometry

NASA Astrophysics Data System (ADS)

Walgraeve, Christophe; Chantara, Somporn; Sopajaree, Khajornsak; De Wispelaere, Patrick; Demeestere, Kristof; Van Langenhove, Herman

2015-04-01

An analytical method using gas chromatography high resolution mass spectrometry was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 oxygenated PAHs (of which 4 diketones, 3 ketones, 4 aldehydes and one anhydride) on atmospheric particulate matter with an aerodynamic diameter less than 10 μm (PM10). The magnetic sector mass spectrometer was run in multiple ion detection mode (MID) with a mass resolution above 10 000 (10% valley definition) and allows for a selective accurate mass detection of the characteristic ions of the target analytes. Instrumental detection limits between 0.04 pg and 1.34 pg were obtained for the PAHs, whereas for the oxy-PAHs they ranged between 0.08 pg and 2.13 pg. Pressurized liquid extraction using dichloromethane was evaluated and excellent recoveries ranging between 87% and 98% for the PAHs and between 74% and 110% for 10 oxy-PAHs were obtained, when the optimum extraction temperature of 150 °C was applied. The developed method was finally used to determine PAHs and oxy-PAHs concentration levels from particulate matter samples collected in the wet season at 4 different locations in Chiang Mai, Thailand (n = 72). This study brings forward the first concentration levels of oxy-PAHs in Thailand. The median of the sum of the PAHs and oxy-PAHs concentrations was 3.4 ng/m3 and 1.1 ng/m3 respectively, which shows the importance of the group of the oxy-PAHs as PM10 constituents. High molecular weight PAHs contributed the most to the ∑PAHs. For example, benzo[ghi]perylene was responsible for 30-44% of the ∑PAHs. The highest contribution to ∑oxy-PAHs came from 1,8-napthalic anhydride (26-78%), followed by anthracene-9,10-dione (4-27%) and 7H-benzo[de]anthracene-7-one (6-26%). Indications of the degradation of PAHs and/or formation of oxy-PAHs were observed.

Performance of PAHs emission from bituminous coal combustion.

PubMed

Yan, Jian-Hua; You, Xiao-Fang; Li, Xiao-Dong; Ni, Ming-Jiang; Yin, Xue-Feng; Cen, Ke-Fa

2004-12-01

Carcinogenic and mutagenic polycyclic aromatic hydrocarbons (PAHs) generated in coal combustion have caused great environmental health concern. Seventeen PAHs (16 high priority PAHs recommended by USEPA plus Benzo[e]pyrene) present in five raw bituminous coals and released during bituminous coal combustion were studied. The effects of combustion temperature, gas atmosphere, and chlorine content of raw coal on PAHs formation were investigated. Two additives (copper and cupric oxide) were added when the coal was burned. The results indicated that significant quantities of PAHs were produced from incomplete combustion of coal pyrolysis products at high temperature, and that temperature is an important causative factor of PAHs formation. PAHs concentrations decrease with the increase of chlorine content in oxygen or in nitrogen atmosphere. Copper and cupric oxide additives can promote PAHs formation (especially the multi-ring PAHs) during coal combustion.

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

Contaminants as habitat disturbers: PAH-driven drift by Andean paramo stream insects.

PubMed

Araújo, Cristiano V M; Moreira-Santos, Matilde; Sousa, José P; Ochoa-Herrera, Valeria; Encalada, Andrea C; Ribeiro, Rui

2014-10-01

Contaminants can behave as toxicants, when toxic effects are observed in organisms, as well as habitat disturbers and fragmentors, by triggering avoidance responses and generating less- or uninhabited zones. Drift by stream insects has long been considered a mechanism to avoid contamination by moving to most favorable habitats. Given that exploration and transportation of crude oil represent a threat for surrounding ecosystems, the key goal of the present study was to assess the ability of autochthonous groups of aquatic insects from the Ecuadorian paramo streams to avoid by drift different concentrations of polycyclic aromatic hydrocarbons (PAH) contained in the soluble fraction of locally transported crude oil. In the laboratory, different groups of insects were exposed to PAH for 12h. Three different assays, which varied in taxa and origin of the organisms, concentrations of PAH (0.6-38.8µgL(-1)), and environment settings (different levels of refuge and flow) were performed. For Anomalocosmoecus palugillensis (Limnephilidae), drift was a major cause of population decline in low concentration treatments but at higher concentrations mortality dominated. PAH was highly lethal, even at lower concentrations, for Chironomidae, Grypopterygidae (Claudioperla sp.) and Hydrobiosidae (Atopsyche sp.), and, therefore, no conclusion about drift can be drawn for these insects. Contamination by PAH showed to be a threat for benthic aquatic insects from Ecuadorian paramo streams as it can cause a population decline due to avoidance by drift and mortality. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Urban sprawl leaves its PAH signature

USGS Publications Warehouse

Van Metre, P.C.; Mahler, B.J.; Furlong, E.T.

2000-01-01

The increasing vehicle traffic associated with urban sprawl in the United States is frequently linked to degradation of air quality, but its effect on aquatic sediment is less well-recognized. This study evaluates trends in PAHs, a group of contaminants with multiple urban sources, in sediment cores from 10 reservoirs and lakes in six U.S. metropolitan areas. The watersheds chosen represent a range in degree and age of urbanization. Concentrations of PAHs in all 10 reservoirs and lakes increased during the past 20-40 years. PAH contamination of the most recently deposited sediment at all sites exceeded sediment-quality guidelines established by Environment Canada, in some cases by several orders of magnitude. These results add a new chapter to the story told by previous coring studies that reported decreasing concentrations of PAHs after reaching highs in the 1950s. Concurrent with the increase in concentrations is a change in the assemblage of PAHs that indicates the increasing trends are driven by combustion sources. The increase in PAH concentrations tracks closely with increases in automobile use, even in watersheds that have not undergone substantial changes in urban land-use levels since the 1970s.The increasing vehicle traffic associated with urban sprawl in the United States is frequently linked to degradation of air quality, but its effect on aquatic sediment is less well-recognized. This study evaluates trends in PAHs, a group of contaminants with multiple urban sources, in sediment cores from 10 reservoirs and lakes in six U.S. metropolitan areas. The watersheds chosen represent a range in degree and age of urbanization. Concentrations of PAHs in all 10 reservoirs and lakes increased during the past 20-40 years. PAH contamination of the most recently deposited sediment at all sites exceeded sediment-quality guidelines established by Environment Canada, in some cases by several orders of magnitude. These results add a new chapter to the story told by

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.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Association between mutation spectra and stable and unstable DNA adduct profiles in Salmonella for benzo[a]pyrene and dibenzo[a,l]pyrene.

PubMed

DeMarini, David M; Hanley, Nancy M; Warren, Sarah H; Adams, Linda D; King, Leon C

2011-09-01

Benzo[a]pyrene (BP) and dibenzo[a,l]pyrene (DBP) are two polycyclic aromatic hydrocarbons (PAHs) that exhibit distinctly different mutagenicity and carcinogenicity profiles. Although some studies show that these PAHs produce unstable DNA adducts, conflicting data and arguments have been presented regarding the relative roles of these unstable adducts versus stable adducts, as well as oxidative damage, in the mutagenesis and tumor-mutation spectra of these PAHs. However, no study has determined the mutation spectra along with the stable and unstable DNA adducts in the same system with both PAHs. Thus, we determined the mutagenic potencies and mutation spectra of BP and DBP in strains TA98, TA100 and TA104 of Salmonella, and we also measured the levels of abasic sites (aldehydic-site assay) and characterized the stable DNA adducts ((32)P-postlabeling/HPLC) induced by these PAHs in TA104. Our results for the mutation spectra and site specificity of stable adducts were consistent with those from other systems, showing that DBP was more mutagenic than BP in TA98 and TA100. The mutation spectra of DBP and BP were significantly different in TA98 and TA104, with 24% of the mutations induced by BP in TA98 being complex frameshifts, whereas DBP produced hardly any of these mutations. In TA104, BP produced primarily GC to TA transversions, whereas DBP produced primarily AT to TA transversions. The majority (96%) of stable adducts induced by BP were at guanine, whereas the majority (80%) induced by DBP were at adenine. Although BP induced abasic sites, DBP did not. Most importantly, the proportion of mutations induced by DBP at adenine and guanine paralleled the proportion of stable DNA adducts induced by DBP at adenine and guanine; however, this was not the case for BP. Our results leave open a possible role for unstable DNA adducts in the mutational specificity of BP but not for DBP. Published by Elsevier B.V.

Do 16 Polycyclic Aromatic Hydrocarbons Represent PAH Air Toxicity?

PubMed Central

Samburova, Vera; Zielinska, Barbara; Khlystov, Andrey

2017-01-01

Estimation of carcinogenic potency based on analysis of 16 polycyclic aromatic hydrocarbons (PAHs) ranked by U.S. Environmental Protection Agency (EPA) is the most popular approach within scientific and environmental air quality management communities. The majority of PAH monitoring projects have been focused on particle-bound PAHs, ignoring the contribution of gas-phase PAHs to the toxicity of PAH mixtures in air samples. In this study, we analyzed the results of 13 projects in which 88 PAHs in both gas and particle phases were collected from different sources (biomass burning, mining operation, and vehicle emissions), as well as in urban air. The aim was to investigate whether 16 particle-bound U.S. EPA priority PAHs adequately represented health risks of inhalation exposure to atmospheric PAH mixtures. PAH concentrations were converted to benzo(a)pyrene-equivalent (BaPeq) toxicity using the toxic equivalency factor (TEF) approach. TEFs of PAH compounds for which such data is not available were estimated using TEFs of close isomers. Total BaPeq toxicities (∑88BaPeq) of gas- and particle-phase PAHs were compared with BaPeq toxicities calculated for the 16 particle-phase EPA PAH (∑16EPABaPeq). The results showed that 16 EPA particle-bound PAHs underrepresented the carcinogenic potency on average by 85.6% relative to the total (gas and particle) BaPeq toxicity of 88 PAHs. Gas-phase PAHs, like methylnaphthalenes, may contribute up to 30% of ∑88BaPeq. Accounting for other individual non-EPA PAHs (i.e., benzo(e)pyrene) and gas-phase PAHs (i.e., naphthalene, 1- and 2-methylnaphthalene) will make the risk assessment of PAH-containing air samples significantly more accurate. PMID:29051449

Do 16 Polycyclic Aromatic Hydrocarbons Represent PAH Air Toxicity?

PubMed

Samburova, Vera; Zielinska, Barbara; Khlystov, Andrey

2017-08-15

Estimation of carcinogenic potency based on analysis of 16 polycyclic aromatic hydrocarbons (PAHs) ranked by U.S. Environmental Protection Agency (EPA) is the most popular approach within scientific and environmental air quality management communities. The majority of PAH monitoring projects have been focused on particle-bound PAHs, ignoring the contribution of gas-phase PAHs to the toxicity of PAH mixtures in air samples. In this study, we analyzed the results of 13 projects in which 88 PAHs in both gas and particle phases were collected from different sources (biomass burning, mining operation, and vehicle emissions), as well as in urban air. The aim was to investigate whether 16 particle-bound U.S. EPA priority PAHs adequately represented health risks of inhalation exposure to atmospheric PAH mixtures. PAH concentrations were converted to benzo(a)pyrene-equivalent (BaPeq) toxicity using the toxic equivalency factor (TEF) approach. TEFs of PAH compounds for which such data is not available were estimated using TEFs of close isomers. Total BaPeq toxicities (∑ 88 BaPeq) of gas- and particle-phase PAHs were compared with BaPeq toxicities calculated for the 16 particle-phase EPA PAH (∑ 16EPA BaPeq). The results showed that 16 EPA particle-bound PAHs underrepresented the carcinogenic potency on average by 85.6% relative to the total (gas and particle) BaPeq toxicity of 88 PAHs. Gas-phase PAHs, like methylnaphthalenes, may contribute up to 30% of ∑ 88 BaPeq. Accounting for other individual non-EPA PAHs (i.e., benzo(e)pyrene) and gas-phase PAHs (i.e., naphthalene, 1- and 2-methylnaphthalene) will make the risk assessment of PAH-containing air samples significantly more accurate.

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.

Mid-Infrared Silicate Dust Features in Seyfert 1 Spectra

NASA Astrophysics Data System (ADS)

Thompson, Grant D.; Levenson, N. A.; Sirocky, M. M.; Uddin, S.

2007-12-01

Silicate dust emission dominates the mid-infrared spectra of galaxies, and the dust produces two spectral features, at 10 and 18 μm. These features' strengths (in emission or absorption) and peak wavelengths reveal the geometry of the dust distribution, and they are sensitive to the dust composition. We examine mid-infrared spectra of 32 Seyfert 1 active galactic nuclei (AGN), observed with the Infrared Spectrograph aboard the Spitzer Space Telescope. In the spectra, we typically find the shorter-wavelength feature in emission, at an average peak wavelength of 10.0 μm, although it is known historically as the "9.7 μm" feature. In addition, peak wavelength increases with feature strength. The 10 and 18 μm feature strengths together are sensitive to the dust geometry surrounding the central heating engine. Numerical calculations of radiative transfer distinguish between clumpy and smooth distributions, and we find that the surroundings of these AGN (the obscuring "tori" of unified AGN schemes) are clumpy. Polycyclic aromatic hydrocarbon (PAH) features are associated with star formation, and we find strong PAH emission (luminosity ≥ 1042 erg/s) in only four sources, three of which show independent evidence for starbursts. We will explore the effects of luminosity on dust geometry and chemistry in a comparison sample of quasars. We acknowledge work supported by the NSF under grant number 0237291.

Analysis of Absorption Spectra of Polycyclic Aromatic Hydrocarbons in Gaseous- and Particle- Phase Emissions from Peat Fuel Combustion Under Controlled Conditions

NASA Astrophysics Data System (ADS)

Connolly, J. I.; Samburova, V.; Moosmüller, H.; Khlystov, A.

2015-12-01

Biomass and fossil fuel burning processes emit important organic pollutants called polycyclic aromatic hydrocarbons (PAHs) into the atmosphere. Smoldering combustion of peat is one of the largest contributors (up to 70%) of carbonaceous species and, therefore, it may be one of the main sources of these PAHs. PAHs can be detrimental to health, they are known to be potent mutagens and suspected carcinogens. They may also contribute to solar light absorption as the particles absorb in the blue and near ultraviolet (UV) region of the solar spectrum ("brown carbon" species). There is very little knowledge and large ambiguity regarding the contribution of PAHs to optical properties of organic carbon (OC) emitted from smoldering biomass combustion. This study focuses on quantifying and analyzing PAHs emitted from peat smoldering combustion to gain more knowledge on their optical properties. Five peat fuels collected in different regions of the world (Russia, USA) were burned under controlled conditions (e.g., relative humidity, combustion efficiency, fuel-moisture content) at the Desert Research Institute Biomass Burning facility (Reno, NV, USA). Combustion aerosols collected on TIGF filters followed by XAD resin cartridges were extracted and analyzed for gas-phase (semi-volatile) and particle-phase PAHs. Filter and XAD samples were extracted separately with dichloromethane followed by acetone using Accelerated Solvent Extractor (ACE 300, Dionex). To determine absorption properties, absorption spectra of extracts and standard PAHs were recorded between 190 and 900 nm with a UV/VIS spectrophotometer (PerkinElmer, Lambda 650). This poster will discuss the potential contribution of PAHs to brown carbon emitted from peat combustion and give a brief comparison with absorption spectra from biomass burning aerosols.

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygenated-PAHs, nitrated-PAHs and azaarenes) in size-fractionated particles emitted in an urban road tunnel

NASA Astrophysics Data System (ADS)

Alves, C. A.; Vicente, A. M. P.; Gomes, J.; Nunes, T.; Duarte, M.; Bandowe, B. A. M.

2016-11-01

A sampling campaign of size segregated particulate matter (PM0.5, PM0.5-1, PM1-2.5 and PM2.5-10) was carried out at two sites, one in a road tunnel (Braga, Portugal) and another at an urban background location in the neighbourhood. Particle-bound polycyclic aromatic compounds were extracted with organic solvents and analysed by gas chromatography-mass spectrometry. Twenty six parent and alkyl-polycyclic aromatic hydrocarbons (PAHs), 4 azaarenes (AZAs), 15 nitrated and 15 oxygenated derivatives (NPAHs and OPAHs) were analysed. On average, submicron particles (PM1) in the tunnel comprised 93, 91, 96 and 71% of the total PAHs, OPAHs, NPAHs and AZAs mass in PM10, respectively. Tunnel to outdoor PAH concentration ratios between 10 and 14 reveal the strong contribution of fresh exhaust emissions to the PM loads. The dominant PAHs in the tunnel were pyrene, retene and benzo[ghi]perylene, accounting for 20, 17 and 8% of the total PAH levels in PM10, respectively. Isomer ratios indicated the importance of unburnt fuel as a significant PAH source. The only NPAH consistently present in all samples was 5-nitroacenaphthene. Indanone and 1,8-naphthalic anhydride were the most abundant OPAHs, accounting for 25 and 17% of the total concentrations of this organic class, respectively. Other abundant OPAHs were 1,4-naphthoquinone, 9-fluorenone, 1,2-acenaphthylenequinone and 7H-benz[de]anthracene-7-one. Individual emission factors (μg veh- 1 km- 1) were estimated and compared with those obtained in other tunnel studies.

PAH body burden and biomarker responses in mussels (Mytilus edulis) exposed to produced water from a North Sea oil field: laboratory and field assessments.

PubMed

Sundt, Rolf C; Pampanin, Daniela M; Grung, Merete; Baršienė, Janina; Ruus, Anders

2011-07-01

In order to study the impact of produced water (PW) from a North Sea oil field on blue mussels (Mytilus edulis), chemical and biological markers were selected. A laboratory exposure (0.125%, 0.25% and 0.5% of PW) and a field study (6 stations 0.2-2 km from a PW discharge point) were conducted. In the laboratory study, PAH bioaccumulation increased in mussel soft tissue even at the lowest exposure dose. Micronuclei frequency demonstrated a dose-response pattern, whereas lysosomal membrane stability showed tendency towards a dose-response pattern. The same markers were assessed in the field study, biomarker analyses were consistent with the contamination level, as evaluated by mussel polycyclic aromatic hydrocarbons body burden. Overall, obtained results confirmed the value of an ecotoxicological approach for a scientifically sound characterisation of biological effects induced by offshore oilfield operational discharges. Copyright © 2011 Elsevier Ltd. All rights reserved.

Formation of nitro-PAHs from the heterogeneous reaction of ambient particle-bound PAHs with NO3/N2O5

NASA Astrophysics Data System (ADS)

Zimmermann, K.; Jariyasopit, N.; Simonich, S. L.; Atkinson, R.; Arey, J.

2012-12-01

Polycyclic aromatic hydrocarbons (PAHs) and their nitrated derivatives (nitro-PAHs) have been shown to be mutagenic in bacterial and mammalian assays and are classified as probable human carcinogens. Semi-volatile PAHs partition between the gas and particulate phases, depending on their liquid-phase vapor pressures and ambient temperatures. These PAHs have been extensively measured in ambient particulate matter and can ultimately undergo long-range transport from source regions (e.g., China to the western USA) (1). During transport these particle-bound PAHs may undergo reaction with NO3/N2O5 to form nitro-PAH derivatives. Previous studies of heterogeneous nitration of PAHs have used particles composed of graphite, diesel soot, and wood smoke (2-4). This study investigates the heterogeneous formation of nitro-PAHs from ambient particle-bound PAHs from Beijing, China and sites located within the Los Angeles air basin. These ambient particle samples, along with filters coated with isotopically labeled PAHs, were exposed to a mix of NO2/NO3/N2O5 in a 7000 L Teflon chamber, with analysis focused on the heterogeneous formation of molecular weight 247 and 273 nitro-PAHs. The heterogeneous formation of certain nitro-PAHs (including1-nitropyrene and 1- and 2-nitrotriphenylene) was observed for some, but not all, ambient samples. Formation of nitro-PAHs typically formed through gas-phase reactions (2-nitrofluoranthene and 2-nitropyrene) was not observed. The effect of particle age and local photochemical conditions during sampling on the degree of nitration in environmental chamber reactions, as well as ambient implications, will be presented. 1. Primbs, T.; Simonich, S.; Schmedding, D.; Wilson, G.; Jaffe, D.; Takami, A.; Kato, S.; Hatakeyama, S.; Kajii, Y. Environ. Sci. Technol. 2007, 41, 3551-3558. 2. Esteve, W.; Budzinski, H.; Villenave, E. Atmospheric Environment 2004, 38, 6063-6072. 3. Nguyen, M.; Bedjanian, Y.; Guilloteau, A. Journal of Atmospheric Chemistry 2009, 62

Investigating the Chemical Pathways to PAH- and PANH-Based Aerosols in Titan's Atmospheric chemistry

NASA Technical Reports Server (NTRS)

Sciamma-O'Brien, Ella Marion; Contreras, Cesar; Ricketts, Claire Louise; Salama, Farid

2011-01-01

A complex organic chemistry between Titan's two main constituents, N2 and CH4, leads to the production of more complex molecules and subsequently to solid organic aerosols. These aerosols are at the origin of the haze layers giving Titan its characteristic orange color. In situ measurements by the Ion Neutral Mass Spectrometer (INMS) and Cassini Plasma Spectrometer (CAPS) instruments onboard Cassini have revealed the presence of large amounts of neutral, positively and negatively charged heavy molecules in the ionosphere of Titan. In particular, benzene (C6H6) and toluene (C6H5CH3), which are critical precursors of polycyclic aromatic hydrocarbon (PAH) compounds, have been detected, suggesting that PAHs might play a role in the production of Titan s aerosols. Moreover, results from numerical models as well as laboratory simulations of Titan s atmospheric chemistry are also suggesting chemical pathways that link the simple precursor molecules resulting from the first steps of the N2-CH4 chemistry (C2H2, C2H4, HCN ...) to benzene, and to PAHs and nitrogen-containing PAHs (or PANHs) as precursors to the production of solid aerosols.

Variation in PAH patterns in road runoff.

PubMed

Aryal, Rupak; Furumai, Hiroaki; Nakajima, Fumiyuki; Beecham, Simon

2013-01-01

Twelve particle-bound polycyclic aromatic hydrocarbons (PAHs) were measured in the first flush regime of road runoff during nine events in Winterthur in Switzerland. The total PAH contents ranged from 17 to 62 μg/g. The PAH patterns measured at different time intervals during the first flush periods were very similar within each event irrespective of variation in suspended solids (SS) concentration within the first flush regime. However, the PAH patterns were different from event to event. This indicates that the environment plays an important role in PAH accumulation in SS. A toxicity identification evaluation approach using a toxicity equivalency factor (TEF) was applied to compare toxicities in the different events. The TEFs were found to be between 8 and 33 μg TEQ g(-1) (TEQ: toxic equivalent concentration). In some cases, two events having similar total PAH contents showed two fold toxicity differences.

Optimization of Polycyclic Aromatic Hydrocarbon (PAH) Extraction Efficiency Parameters for Sub- and Supercritical Water Extraction (SCWE) Instrument

NASA Technical Reports Server (NTRS)

Okada, Asahi A.

2005-01-01

Polycyclic aromatic hydrocarbons are a class of molecules composed of multiple, bonded benzene rings. As PAHS are believed to be present on Mars, positive confirmation of their presence on Mars is highly desirable. To extract PAHS, which have low volatility, a fluid extraction method is ideal, and one that does not utilize organic solvents is especially ideal for in situ instrumental analysis. The use of water as a solvent, which at subcritical pressures and temperatures is relatively non-Polar, has significant potential. As SCWE instruments have not yet been commercialized, all instruments are individually-built research prototypes: thus, initial efforts were intended to determine if extraction efficiencies on the JPL-built laboratory-scale SCWE instrument are comparable to differing designs built elsewhere. Samples of soil with certified reference concentrations of PAHs were extracted using SCWE as well as conventional Soxhlet extraction. Continuation of the work would involve extractions on JPL'S newer, portable SCWE instrument prototype to determine its efficiency in extracting PAHs.

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

PAHs in polystyrene food contact materials: An unintended consequence.

PubMed

Li, Si-Qi; Ni, Hong-Gang; Zeng, Hui

2017-12-31

Eight low-ring PAHs were detected in 21 polystyrene (PS) food contact materials (FCMs) samples while high-ring PAHs (>4 rings) were not found. This is because the reaction pathway for formation of high-ring PAHs consists of more steps than it does for low-high PAHs. The concentrations of Σ 8 PAH were from 18.9±5.16ng/g for product colorless fruit fork to 476±52.0ng/g for foam instant noodle container. These data were far beyond levels of PAHs in other plastics. Of the eight PAHs detected, Phe had the highest average concentration, followed by Nap. These two PAHs collectively accounted for over 80% of the Σ 8 PAH concentrations in all PS FCMs. Levels of Σ 8 PAH in expanded PS FCMs were higher than those in extruded ones due to utilization of foaming agent. The concentrations of Σ 8 PAH were lower in colorless PS FCMs than in colored ones. Auxochromes and chromophores contributed to the change of short-chain hydrocarbons to aromatic hydrocarbon. Simulated migration values of PAHs from PS FCMs to food varied widely. The migration value of Σ 8 PAH with maximum probability was below 10ng/g, which the maximum tolerated migration level for substance according to the European Union standards. However, higher migration values were possible and the potential health risk should still be concerned because the simulated migration displayed a log-normal distribution. Furthermore, water was used as food simulant would always lead to an underestimate of PAHs migration to real daily food, and then lead to an underestimate of risk. Copyright © 2017 Elsevier B.V. All rights reserved.

Growth of nano hexagon-like flake arrays cerium carbonate created with PAH as the substrate

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

Li, M., E-mail: limei@imust.cn; School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Department of Inorganic and Metalloid Materials, Key Laboratory of New Technologies of Modern Metallurgy and Application of Rare Materials, Baotou 014010; Hu, Y.H., E-mail: bthyh@163.com

Petals-like Ce{sub 2}(CO{sub 3}){sub 3} on Ce{sub 2}(CO{sub 3}){sub 3} nano hexagon-like flake arrays have been precipitatingly fabricated using PAH substrates. By changing the way of feeding, PAH concentration and aging time, petals-like Ce{sub 2}(CO{sub 3}){sub 3} was created best when adding PAH into the Ce(NO{sub 3}){sub 3} solution, joined (NH{sub 4}){sub 2}CO{sub 3} solution along with mixing, PAH concentration is 0.9 g/L, aging time is 4 h. A growth mechanism was proposed to account for the growth of the petals-like Ce{sub 2}(CO{sub 3}){sub 3} with PAH as the substrate. Poly allylamine hydrochloride (PAH) is as template agent which formsmore » π-allyl complex with Ce{sup 3+} and controls the morphology of Ce{sub 2}(CO{sub 3}){sub 3} particle. PAH and Ce{sup 3+} form π-allyl complex, and then induce the formation of Ce{sub 2}(CO{sub 3}){sub 3} crystal nucleus. And infrared spectrum analysis verified. XRD show that after adding PAH which is adsorbed on the crystal plane, the growth of Ce{sub 2}(CO{sub 3}){sub 3} crystal is inhibited on (2 4 2), the growth is promoted on (2 0 2) which is differentiated into the new (1 5 1), (2 2 2) is unchanged, Ce{sub 2}(CO{sub 3}){sub 3} crystal is accumulated petals shape by hexagon-like flake. UV absorption spectra show that CeO{sub 2} as prepared precursor Ce{sub 2}(CO{sub 3}){sub 3} after calcinations in air at high temperatures, the petal-like CeO{sub 2} has strong UV absorption and reflection effects, and absorption interval changed significantly by the move to UVA from UVB. - Graphical abstract: Each Ce-atom connects three Cl-atoms and three allyls in three dimensional spaces. To take the plane as a reference plane which is arrayed with three Ce-atom as equilateral triangle. The triangular each vertex is Ce-atom, the triangular center place is Cl-atom, the equilateral triangle which is mutually perpendicular with Ce-triangle surface and the inclined angle is 60° is made up with three Cl-atoms. - Highlights: �

ISTA 14-in-situ accumulation of PAHs in low-density polyethylene membranes in sediment.

PubMed

Devault, Damien A; Combe, Matthieu; Gourlay-Francé, Catherine

2010-10-01

The use of passive samplers for the assessment of organic contaminants has been extended to solid matrixes for the past decade. Passive sampling is usually applied to sediment in laboratory experiments involving significant upheaval, whereas in-situ experiments remain rare. In this study, low-density polyethylene (LDPE) strips were deployed within the sediments of a small river contaminated with polycyclic aromatic hydrocarbons (PAHs). LDPE strips were deployed in the 3-cm depth sediment layer. Over a period of 36 days, LDPE strips were regularly retrieved and accumulated PAHs in LDPE were extracted and analyzed. Accumulations of hydrophobic contaminants in LDPE directly exposed in the sediment were observed. Accumulations in LDPE were observed for moderately hydrophobic PAHs with the highest concentrations in the sediment. Low accumulations were observed for more hydrophobic compounds, despite their presence in high concentrations in the sediment. This was explained by very low exchange rates and competitive interactions with particles in the sediment. © 2010 Wiley Periodicals, Inc. Environ Toxicol, 2010.

Ab Initio Determinations of Photoelectron Spectra Including Vibronic Features: An Upper-Level Undergraduate Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Lord, Richard L.; Davis, Lisa; Millam, Evan L.; Brown, Eric; Offerman, Chad; Wray, Paul; Green, Susan M. E.

2008-01-01

We present a first-principles determination of the photoelectron spectra of water and hypochlorous acid as a laboratory exercise accessible to students in an undergraduate physical chemistry course. This paper demonstrates the robustness and user-friendliness of software developed for the Franck-Condon factor calculation. While the calculator is…

PAH related effects on fish in sedimentation ponds for road runoff and potential transfer of PAHs from sediment to biota.

PubMed

Grung, Merete; Petersen, Karina; Fjeld, Eirik; Allan, Ian; Christensen, Jan H; Malmqvist, Linus M V; Meland, Sondre; Ranneklev, Sissel

2016-10-01

Road runoff is an important source of pollution to the aquatic environment, and sedimentation ponds have been installed to mitigate effects on the aquatic environment. The purpose of this study was to investigate if a) fish from sedimentation ponds were affected by road pollution and; b) the transfer of PAHs from road runoff material to aquatic organisms was substantial. Minnow from a sedimentation pond (Skullerud) near Oslo (Norway) had higher levels of CYP1A enzyme and DNA stand breaks than minnow from the nearby river, but high concentrations of PAH-metabolites in bile revealed that both populations were highly exposed. Principal component analysis revealed that CYP1A and age of fish were correlated, while levels of PAH-metabolites were not correlated to CYP1A or DNA damage. Minnow from a lake un-affected by traffic had much lower levels of PAH-metabolites than the exposed fish, and also an improved condition. The latter results indicate that fish health was affected by road runoff. A closer investigation of PAH levels of the ecosystems of two sedimentation ponds (Skullerud and Vassum) and nearby environments were conducted. The concentration of the 16 EPA PAHs in sediments of the sedimentation ponds were high (1900-4200ngg(-1)), and even higher levels were observed in plants. Principal component analysis of selected ion chromatograms of PAHs showed a clear separation of plants vs. sediments. The plants preferentially accumulated the high molecular PAHs, both from sedimentation ponds with a petrogenic PAH isomer ratio in sediments; and from a lake with pyrogenic PAH isomer ratio in sediments. Copyright © 2016 Elsevier B.V. All rights reserved.

Laboratory Reflectance Spectra in the Middle-infrared: Effects of Grain Size on Spectral Features

NASA Astrophysics Data System (ADS)

Le Bras, A.; Erard, S.; Fulchignoni, M.

2000-10-01

Since spectral mineral features are sensitive to surface parameters, interpretation of remote-sensing asteroids spectra in terms of mineral composition is not easy nor unique, and laboratory spectra are needed in order to understand the influence of each parameter. We developped an experimental program at IAS, using the 2.5-120 microns interferometer spectrometer, to study the influence of surface parameters on mineral features. We present here the results obtained variing the grain size. We studied grain size effects with two types of terrestrial rocks: anorthosite (bright) and basalte (dark) in the 2-40 microns range. We observed variations of the spectral contrast with grain size, shifts in wavelengths and variations of the intensity of some characteristic spectral features, and appearence of transparency features at wavelengths longer than 8 microns.

Correlations between PAH bioavailability, degrading bacteria, and soil characteristics during PAH biodegradation in five diffusely contaminated dissimilar soils.

PubMed

Crampon, M; Bureau, F; Akpa-Vinceslas, M; Bodilis, J; Machour, N; Le Derf, F; Portet-Koltalo, F

2014-01-01

The natural biodegradation of seven polycyclic aromatic hydrocarbons (PAHs) by native microorganisms was studied in five soils from Normandy (France) from diffusely polluted areas, which can also pose a problem in terms of surfaces and amounts of contaminated soils. Bioavailability tests using cyclodextrin-based extractions were performed. The natural degradation of low molecular weight (LMW) PAHs was not strongly correlated to their bioavailability due to their sorption to geosorbents. Conversely, the very low degradation of high molecular weight (HMW) PAHs was partly correlated to their poor availability, due to their sorption on complexes of organic matter and kaolinites or smectites. A principal component analysis allowed us to distinguish between the respective degradation behaviors of LMW and HMW PAHs. LMW PAHs were degraded in less than 2-3 months and were strongly influenced by the relative percentage of phenanthrene-degrading bacteria over total bacteria in soils. HMW PAHs were not significantly degraded, not only because they were less bioavailable but also because of a lack of degrading microorganisms. Benzo[a]pyrene stood apart since it was partly degraded in acidic soils, probably because of a catabolic cooperation between bacteria and fungi.

Comparison of spatial and temporal variations in p-PAH, BC, and p-PAH/BC ratio in six US counties

NASA Astrophysics Data System (ADS)

Han, Inkyu; Ramos-Bonilla, Juan P.; Rule, Ana M.; Mihalic, Jana N.; Polyak, Lisa M.; Breysse, Patrick N.; Geyh, Alison S.

2011-12-01

An ambient air monitoring campaign was performed in six counties (Sacramento, CA; Maricopa, AZ; Anoka, MN; Jefferson, KY; Harris, TX; and Pinellas, FL) between January 2008 and September 2009. The purpose of this paper is to compare the spatial and temporal variability of black carbon (BC) and particle-bound polycyclic aromatic hydrocarbons (p-PAHs), across these counties using continuous monitoring instruments - an Aethalometer and a Photoelectric Aerosol Sensor reporting in units of μg m -3 and fA, respectively. We explored temporal trends in these measurements to assess the potential impact of local combustion sources on air quality. Median BC concentrations ranged from 0.13 to 0.53 μg m -3; and median p-PAH values ranged from 0.31 to 4.18 fA. Hourly BC and p-PAH were elevated during morning rush hour and rapidly decreased later in the morning. Nighttime increases in BC and p-PAH were also observed in most counties. Diurnal patterns of BC and p-PAH were different on weekdays compared to weekends. Profiles of hourly ratios of p-PAH/BC in combination with meteorological data can provide insight into potential sources across the sites. Hourly ratios of p-PAH/BC which peaked during early morning and late afternoon hours suggest a dominating contribution of motor vehicle sources in four of the six counties. In two counties, hourly ratios remained elevated for several hours after rush hour and did not show a distinctive peak suggesting additional sources of BC and p-PAH. Such profiles were seen in both Jefferson KY and Harris TX, and may be attributed to coal combustion, petro-chemical industry and shipping activities, respectively. These results suggest that measurements of BC and p-PAH, combined with meteorological information and emission data are potentially useful to identify combustion sources impacting air quality. More research combining BC and p-PAH measurements with detailed source apportionment data is needed to more fully evaluate the utility of these

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.

Degradation of polycyclic aromatic hydrocarbons (PAHs) during Sphagnum litters decay.

PubMed

Wang, Zucheng; Liu, Shasha; Bu, Zhao-Jun; Wang, Shengzhong

2018-04-28

The dynamics of polycyclic aromatic hydrocarbon (PAH) degradation in Sphagnum litters and the decomposition of the litters were investigated. PAH concentration decreased to approximately half of the initial concentration as Sphagnum litters decayed. The initial PAH concentration was 489.2 ± 72.2 ng g -1 , and the concentration after 120 days of incubation was 233.0 ± 5.8 ng g -1 . The different PAH compositions changed concentrations at different times. The low-molecular-weight (LMW) and high-molecular-weight (HMW) PAHs started to be degraded after incubation and after 40 days of incubation, respectively. PAH concentrations in the Sphagnum litters correlated with the total organic carbon (TOC) content (p < 0.05), indicating that PAHs were associated with the TOC of the Sphagnum litters and were degraded as organic matter decayed. The positive relationship between LMW PAH concentration and the soluble carbohydrate content (p < 0.05) indicated that LMW PAHs and the readily decomposed organic carbon fractions were cometabolized, or that LMW PAHs were mainly absorbed by soluble carbohydrate. The weak negative correlation between fulvic acid (FA) and PAH concentrations (p < 0.1) indicated that FA may enhance PAH degradation. Redundancy analysis suggested that the contents of both soluble carbohydrate and cellulose significantly affected the changes in PAH concentrations (p < 0.05), and that FA content and C/N ratios may also contribute to the changes in PAH concentrations (p < 0.1). However, the polyphenol that was related to microbial activities was not associated with changes in PAH concentrations. These results suggested that litter quality is more important than microbial activities in PAH degradation in Sphagnum litters.

Mineralization Of PAHs In Coal-Tar Impacted Aquifer Sediments And Associated Microbial Community Structure Investigated With FISH

EPA Science Inventory

The microbial community structure and mineralization of polycyclic aromatic hydrocarbons (PAHs) in a coal-tar contaminated aquifer were investigated spatially using fluorescence in situ hybridization (FISH) and in laboratory-scale incubations of the aquifer sediments. DAPI-detect...

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

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.

Laboratory measurements of radiance and reflectance spectra of dilute secondary-treated sewage sludge

NASA Technical Reports Server (NTRS)

Witte, W. G.; Usry, J. W.; Whitlock, C. H.; Gurganus, E. A.

1977-01-01

The National Aeronautics and Space Administration (NASA), in cooperation with the Environmental Protection Agency (EPA) and the National Oceanic and Atmospheric Administration (NOAA), conducted a research program to evaluate the feasibility of remotely monitoring ocean dumping of waste products such as acid and sewage sludge. One aspect of the research program involved the measurements of upwelled spectral signatures for sewage-sludge mixtures of different concentrations in an 11600-liter tank. This paper describes the laboratory arrangement and presents radiance and reflectance spectra in the visible and near-infrared ranges for concentrations ranging from 9.7 to 180 ppm of secondary-treated sewage sludge mixed with two types of base water. Results indicate that upwelled radiance varies in a near-linear manner with concentration and that the sludge has a practically flat signal response between 420 and 970 nm. Reflectance spectra were obtained for the sewage-sludge mixtures at all wavelengths and concentrations.

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.

Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs in the coastal seawater, surface sediment and oyster from Dalian, Northeast China.

PubMed

Hong, Wen-Jun; Jia, Hongliang; Li, Yi-Fan; Sun, Yeqing; Liu, Xianjie; Wang, Luo

2016-06-01

A total of 46 polycyclic aromatic hydrocarbons (PAHs, 21 parent and 25 alkylated) were determined in seawater, surface sediment and oyster from coastal area of Dalian, North China. The concentration of Σ46PAHs in seawater, sediment, and oyster were 136-621 ng/L, 172-4700 ng/g dry weight (dw) and 60.0-129 ng/g wet weight (ww) in winter, and 65.0-1130 ng/L, 71.1-1090 ng/g dw and 72.8-216 ng/g ww in summer, respectively. High PAH levels were found in industrial area both in winter and summer. Selected PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism and the results indicate that surface sediment from all sampling sites have a low to medium ecotoxicological risk. Daily intake of PAHs via oyster as seafood by humans were estimated and the results indicated that oyster intake would not pose a health risk to humans even 30 days after a oil spill accident near by. Water-sediment exchange analysis showed that, both in winter and summer, the fluxes for most high molecular weight PAHs were from seawater to sediment, while for low molecular weight PAHs, an equilibrium was reached between seawater and sediment. Copyright © 2016 Elsevier Inc. All rights reserved.

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

PubMed

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

2018-03-01

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

SCAMP and the ASP

NASA Astrophysics Data System (ADS)

Idehara, H.; Carbon, D. F.

2004-12-01

We present two new, publicly available tools to support the examination and interpretation of spectra. SCAMP is a specialized graphical user interface for MATLAB. It allows researchers to rapidly intercompare sets of observational, theoretical, and/or laboratory spectra. Users have extensive control over the colors and placement of individual spectra, and over spectrum normalization from one spectral region to another. Spectra can be interactively assigned to user-defined groups and the groupings recalled at a later time. The user can measure/record positions and intensities of spectral features, interactively spline-fit spectra, and normalize spectra by fitted splines. User-defined wavelengths can be automatically highlighted in SCAMP plots. The user can save/print annotated graphical output suitable for a scientific notebook depicting the work at any point. The ASP is a WWW portal that provides interactive access to two spectrum data sets: a library of synthetic stellar spectra and a library of laboratory PAH spectra. The synthetic stellar spectra in the ASP are appropriate to the giant branch with an assortment of compositions. Each spectrum spans the full range from 2 to 600 microns at a variety of resolutions. The ASP is designed to allow users to quickly identify individual features at any resolution that arise from any of the included isotopic species. The user may also retrieve the depth of formation of individual features at any resolution. PAH spectra accessible through the ASP are drawn from the extensive library of spectra measured by the NASA Ames Astrochemistry Laboratory. The user may interactively choose any subset of PAHs in the data set, combine them with user-defined weights and temperatures, and view/download the resultant spectrum at any user-defined resolution. This work was funded by the NASA Advanced Supercomputing Division, NASA Ames Research Center.

Development of the Pulmonary Arterial Hypertension-Symptoms and Impact (PAH-SYMPACT®) questionnaire: a new patient-reported outcome instrument for PAH.

PubMed

McCollister, Deborah; Shaffer, Shannon; Badesch, David B; Filusch, Arthur; Hunsche, Elke; Schüler, René; Wiklund, Ingela; Peacock, Andrew

2016-06-14

Regulators and clinical experts increasingly recognize the importance of incorporating patient-reported outcomes (PROs) in clinical studies of therapies for pulmonary arterial hypertension (PAH). No PAH-specific instruments have been developed to date in accordance with the 2009 FDA guidance for the development of PROs as endpoints in clinical trials. A qualitative research study was conducted to develop a new instrument assessing PAH symptoms and their impacts following the FDA PRO guidance. A cross-sectional study was conducted at 5 centers in the US in symptomatic PAH patients aged 18-80 years. Concept elicitation was based on 5 focus group discussions, after which saturation of emergent concepts was reached. A PRO instrument for PAH symptoms and their impacts was drafted. To assess the appropriateness of items, instructions, response options, and recall periods, 2 rounds of one-on-one cognitive interviews were conducted, with instrument revisions following each round. Additional interviews tested the usability of an electronic version (ePRO). PRO development considered input from an international Steering Committee, and translatability and lexibility assessments. Focus groups comprised 25 patients (5 per group); 20 additional patients participated in cognitive interviews (10 per round); and 10 participated in usability interviews. Participants had a mean ± SD age of 53.1 ± 15.8 years, were predominantly female (93 %), and were diverse in race/ethnicity, WHO functional class (FC I/II: 56 %, III/IV: 44 %), and PAH etiology (idiopathic: 56 %, familial: 2 %, associated: 42 %). The draft PRO instrument (PAH-SYMPACT®) was found to be clear, comprehensive, and relevant to PAH patients in cognitive interviews. Items were organized in a draft conceptual framework with 16 symptom items in 4 domains (respiratory symptoms, tiredness, cardiovascular symptoms, other symptoms) and 25 impact items in 5 domains (physical activities, daily activities, social

[PAH exposure in asphalt workers].

PubMed

Garattini, Siria; Sarnico, Michela; Benvenuti, Alessandra; Barbieri, P G

2010-01-01

There has been interest in evaluating the potential carcinogenicity of bitumen fumes in asphalt workers since the 1960's. The IARC classified air-refined bitumens as possible human carcinogens, while coal-tar fumes were classified as known carcinogens. Occupational/environmental PAH exposure can be measured by several urinary markers. Urinary 1-OHP has become the most commonly used biological marker of PAH exposure in asphalt workers. The aim of this study was to assess asphalt workers' exposure levels by monitoring 1-OHP urinary excretion and compare this data with those of non-occupationally exposed subjects. We investigated three groups of asphalt workers: 100 in summer 2007, 29 in winter 2007, and 148 during summer 2008 and compared 1-OHP urinary concentrations using Kruskall-Wallis test. Median 1-OHP urinary concentrations during the three biomonitoring sampling periods were 0.65, 0.17 and 0.53 microg/g creatinine respectively. There was a significant difference in 1-OHP values between the three groups (p < 0.001). our study showed that PAH exposure of asphalt workers' is higher than that observed in the general population and in workers in urban areas. Our results suggest that PAH exposure in the three groups studied is not sufficiently kept under control by the use of personal protective equipment and that biomonitoring is useful in evaluating PAH exposure and for risk assessment. Regulations need to be enforced for workers exposed to cancer risk, such as the register of workers exposed to carcinogens.

The Role of Human Aldo-Keto Reductases in the Metabolic Activation and Detoxication of Polycyclic Aromatic Hydrocarbons: Interconversion of PAH Catechols and PAH o-Quinones

PubMed Central

Zhang, Li; Jin, Yi; Huang, Meng; Penning, Trevor M.

2012-01-01

Polycyclic aromatic hydrocarbons (PAH) are ubiquitous environmental pollutants. They are procarcinogens requiring metabolic activation to elicit their deleterious effects. Aldo-keto reductases (AKR) catalyze the oxidation of proximate carcinogenic PAH trans-dihydrodiols to yield electrophilic and redox-active PAH o-quinones. AKRs are also found to be capable of reducing PAH o-quinones to form PAH catechols. The interconversion of o-quinones and catechols results in the redox-cycling of PAH o-quinones to give rise to the generation of reactive oxygen species and subsequent oxidative DNA damage. On the other hand, PAH catechols can be intercepted through phase II metabolism by which PAH o-quinones could be detoxified and eliminated. The aim of the present review is to summarize the role of human AKRs in the metabolic activation/detoxication of PAH and the relevance of phase II conjugation reactions to human lung carcinogenesis. PMID:23162467

Laboratory Far-infrared Spectroscopy Of Terrestrial Phyllosilicates To Support Analysis Of Cosmic Dust Spectra.

NASA Astrophysics Data System (ADS)

Yesiltas, Mehmet; Brusentsova, T.; Peale, R.; Maukonen, D.; Figueiredo, P.; Harlow, G. H.; Ebel, D. S.; Nissinboim, A.; Sherman, K.; Lisse, C. M.

2012-01-01

Poster Abstract: 219th AAS Meeting M. Yesiltas1, T. Brusentsova1, R. E. Peale1, D. Maukonen1, P. Figueiredo1, G. E. Harlow2, D. S. Ebel2, A. Nissinboim2, K. Sherman2, and C. M. Lisse3 Remote spectral detection of hydrated minerals is of general interest in the solar system and dusty circumstellar disks. This paper presents spectroscopy of terrestrial phyllosilicate minerals in the wavelength range 15 - 250 µm to support interpretation of returned data from far-IR space-missions such as the Herschel Space Observatory. The far-IR spectral region beyond 15 micron wavelength is especially diagnostic of mineral composition and crystal structure. Relatively little far-IR spectral data exists in the literature on suitably-characterized naturally-occurring phyllosilicate minerals in the wavelength range 60-210 microns corresponding to the PACS instrument of Herschel Space Observatory. Extending the database of laboratory far-IR spectra of terrestrial mineral analogs is therefore desirable and timely. Seventeen phyllosilicate minerals expected in various astronomical environments were sampled from the American Museum of Natural History for diversity and astrophysical relevancy, based on their identification in Stardust, in stratospheric IDP samples, or in meteorites. These include serpentines (Antigorite and Chrysotile), smectites (Talc, Pyrophyllite, Vermiculite, Montmorillonite, Beidellite, Saponite, Nontronite and Hectorite), chlorites (Clinochlore), micas (Muscovite, Paragonite, Margarite, Clintonite, Biotite and Illite), and kaolinites (Dickite, Nacrite, Kaolinite, Halloysite, Attapulgite and Sepiolite). Spectra of micron-sized powder suspensions in polyethelyne pellets reveal prominent and characteristic far-IR features, which differ significantly in some cases from already published spectra, where available. Acknowledgements : This research was supported by NASA-JPL Contract # 1327221. 1Department of Physics, University of Central Florida, Orlando FL 32816 USA2

DNA damage in marine rock oyster (Saccostrea Cucullata) exposed to environmentally available PAHs and heavy metals along the Arabian Sea coast.

PubMed

Sarker, Subhodeep; Vashistha, Deepti; Saha Sarker, Munmun; Sarkar, A

2018-04-30

Molecular biomarkers are used world wide for quick assessment of the immediate effect of environmental pollution on marine ecosystems. Recently, we evaluated oxidative stress responses of marine rock oyster, Saccostrea cucullata impacted due to polycyclic aromatic hydrocarbons (PAHs) accumulated in their tissues at a few sampling sites along the coast of Goa around the region of the Arabian sea coast, India (Sarkar et al., 2017). Using a combination of partial alkaline unwinding and comet assays, we now report a comprehensive study on the impairment of DNA integrity (DI) in S. cucullata due to exposure to environmentally available PAHs and also heavy metals (Pb, Cd, Cu, Fe and Mn) along the Arabian Sea coast, Goa, India exclusively around the entire coast of Goa. First, we determined significant correlation between DI in S. cucullata and the extent of exposure to and bioaccumulation of different PAH compounds including 2-3 aromatic ring PAHs (R 2 , 0.95), 4-6 aromatic ring PAHs (R 2 , 0.85), oxygenated-PAHs (oxy-PAHs, R 2 , 0.84) and total PAHs (t-PAHs, R 2 , 0.98). Second, we observed dose-dependent decrease in DI in S. cucullata with increasing concentrations of different PAH components in oyster tissues. We substantiated our field observations with appropriate laboratory controls using benzo[a]pyrene (BaP). Third, we performed stepwise multiple regression analyses of different water quality parameters including pH, salinity, temperature, dissolved oxygen (DO), biochemical oxygen demand (BOD), nitrite (NO 2 ), nitrate (NO 3 ), phosphate (PO 4 ), turbidity and also t-PAH-biota, t-PAH-water with DI as the dependent variable. Among all these parameters, only four parameters such as t-PAH-biota in combination with DO, BOD and NO 2 showed significant correlation (R¯ 2 = 0.95) with loss in DI in S. cucullata. Based on these results, we created a map indicating the percentage of DNA damage in S. cucullata exposed to PAHs and heavy metals at each sampling location along

Global time trends in PAH emissions from motor vehicles

NASA Astrophysics Data System (ADS)

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

2011-04-01

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

Biodegradation of PAHs in Soil: Influence of Initial PAHs Concentration

NASA Astrophysics Data System (ADS)

Kamil, N. A. F. M.; Talib, S. A.

2016-07-01

Most studies on biodegradation of Polycyclic Aromatic Hydrocarbons (PAHs) evaluate the effect of initial PAHs concentration in liquid medium. There are limited studies on evaluation in solid medium such as contaminated soil. This study investigated the potential of the bacteria, Corynebacterium urealyticum isolated from municipal sludge in degrading phenanthrene contaminated soil in different phenanthrene concentration. Batch experiments were conducted over 20 days in reactors containing artificially contaminated phenanthrene soil at different concentration inoculated with a bacterial culture. This study established the optimum condition for phenanthrene degradation by the bacteria under nonindigenous condition at 500 mg/kg of initial phenanthrene concentration. High initial concentration required longer duration for biodegradation process compared to low initial concentration. The bacteria can survive for three days for all initial phenanthrene concentrations.

Uptake of PAHs by cabbage root and leaf in vegetable plots near a large coking manufacturer and associations with PAHs in cabbage core.

PubMed

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

2017-08-01

Samples of ambient air (including gaseous and particulate phases), dust fall, surface soil, rhizosphere soil, core (edible part), outer leaf, and root of cabbage from eight vegetable plots near a large coking manufacturer were collected during the harvest period. Concentrations, compositions, and distributions of parent PAHs in different samples were determined. Our results indicated that most of the parent PAHs in air occurred in the gaseous phase, dominated by low molecular weight (LMW) species with two to three rings. Specific isomeric ratios and principal component analysis were employed to preliminarily identify the local sources of parent PAHs emitted. The main emission sources of parent PAHs could be apportioned as a mixture of coal combustion, coking production, and traffic tailing gas. PAH components with two to four rings were prevailing in dust fall, surface soil, and rhizosphere soil. Concentrations of PAHs in surface soil exhibited a significant positive correlation with topsoil TOC fractions. Compositional profiles in outer leaf and core of cabbage, dominated by LMW species, were similar to those in the local air. Overall, the order of parent PAH concentration in cabbage was outer leaf > root > core. Partial correlation analysis and multivariate linear stepwise regression revealed that PAH concentrations in cabbage core were closely associated with PAHs present both in root and in outer leaf, namely, affected by adsorption, then absorption, and translocation of PAHs from rhizosphere soil and ambient air, respectively.

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.

[Polycyclic aromatic hydrocarbons (PAHs) in herbs and fruit teas].

PubMed

Ciemniak, Artur

2005-01-01

Polycyclic aromatic hydrocarbons (PAHs) of which benzo[a]pyrene is the most commonly studied and measured, are fused - ring aromatic compounds formed in both natural and man made processes and are found widely distributed throughout the human environment. PAHs occur as contaminants in different food categories and beverages including water, vegetables, fruit, cereals, oils and fats, barbecued and smoked meat. The sources of PAHs in food are predominantly from environmental pollution and food processing. PAHs emissions from automobile traffic and industry activities were show to influence the PAHs levels in vegetables and fruits. The present study was carried out to determine levels of 16 basic PAHs in herbs and fruit teas. The method was based on the hexane extraction and cleaned up by florisil cartridge. The extracts were analysed by GC-MS. The levels of total PAHs varied from 48,27 microg/kg (hibiscus tea) to 1703 microg/kg (green tea). The highest level of BaP was found in lime tea (74,2 microg/kg).

Polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs and related environmental compounds: biological markers of exposure and effects.

PubMed Central

Talaska, G; Underwood, P; Maier, A; Lewtas, J; Rothman, N; Jaeger, M

1996-01-01

Lung cancer caused by polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs and related environmental agents is a major problem in industrialized nations. The high case-fatality rate of the disease, even with the best supportive treatment, underscores the importance of primary lung cancer prevention. Development of biomarkers of exposure and effects to PAHs and related compounds is now underway and includes measurement of urinary metabolites of specific PAHs as well as detection of protein and DNA adducts as indicators of effective dose. Validation of these markers in terms of total environmental dose requires that concurrent measures of air levels and potential dermal exposure be made. In addition, the interrelationships between PAH biomarkers must be determined, particularly when levels of the marker in surrogate molecules (e.g., protein) or markers from surrogate tissues (e.g., lymphocyte DNA) are used to assess the risk to the target organ, the lung. Two approaches to biomarker studies will be reviewed in this article: the progress made using blood lymphocytes as surrogates for lung tissues and the progress made developing noninvasive markers of carcinogen-DNA adduct levels in lung-derived cells available in bronchial-alveolar lavage and in sputum. Data are presented from studies in which exfoliated urothelial cells were used as a surrogate tissue to assess exposure to human urinary bladder carcinogens in occupational groups. PMID:8933032

Using slow-release permanganate candles to remediate PAH-contaminated water.

PubMed

Rauscher, Lindy; Sakulthaew, Chainarong; Comfort, Steve

2012-11-30

Surface waters impacted by urban runoff in metropolitan areas are becoming increasingly contaminated with polycyclic aromatic hydrocarbons (PAHs). Slow-release oxidant candles (paraffin-KMnO(4)) are a relatively new technology being used to treat contaminated groundwater and could potentially be used to treat urban runoff. Given that these candles only release permanganate when submerged, the ephemeral nature of runoff events would influence when the permanganate is released for treating PAHs. Our objective was to determine if slow-release permanganate candles could be used to degrade and mineralize PAHs. Batch experiments quantified PAH degradation rates in the presence of the oxidant candles. Results showed most of the 16 PAHs tested were degraded within 2-4 h. Using (14)C-labled phenanthrene and benzo(a)pyrene, we demonstrated that the wax matrix of the candle initially adsorbs the PAH, but then releases the PAH back into solution as transformed, more water soluble products. While permanganate was unable to mineralize the PAHs (i.e., convert to CO(2)), we found that the permanganate-treated PAHs were much more biodegradable in soil microcosms. To test the concept of using candles to treat PAHs in multiple runoff events, we used a flow-through system where urban runoff water was pumped over a miniature candle in repetitive wet-dry, 24-h cycles. Results showed that the candle was robust in removing PAHs by repeatedly releasing permanganate and degrading the PAHs. These results provide proof-of-concept that permanganate candles could potentially provide a low-cost, low-maintenance approach to remediating PAH-contaminated water. Copyright © 2012 Elsevier B.V. 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.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

NASA Technical Reports Server (NTRS)

Hudson, R. L.; Loeffler, M. J.; Yocum, K. M.

2017-01-01

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

NASA Astrophysics Data System (ADS)

Hudson, R. L.; Loeffler, M. J.; Yocum, K. M.

2017-02-01

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

Coal-tar pavement sealants might substantially increase children's PAH exposures

USGS Publications Warehouse

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

2012-01-01

Dietary ingestion has been identified repeatedly as the primary route of human exposure to polycyclic aromatic hydrocarbons (PAHs), seven of which are classified as probable human carcinogens (B2 PAHs) by the U.S. EPA. Humans are exposed to PAHs through ingestion of cooked and uncooked foods, incidental ingestion of soil and dust, inhalation of ambient air, and absorption through skin. Although PAH sources are ubiquitous in the environment, one recently identified PAH source stands out: Coal-tar-based pavement sealant—a product applied to many parking lots, driveways, and even playgrounds primarily in the central, southern, and eastern U.S.—has PAH concentrations 100–1000 times greater than most other PAH sources. It was reported recently that PAH concentrations in house dust in residences adjacent to parking lots with coal-tar-based sealant were 25 times higher than in residences adjacent to unsealed asphalt parking lots.

Determination of polycyclic aromatic hydrocarbons (PAHs) in seafood using gas chromatography-mass spectrometry: collaborative study.

PubMed

Mastovska, Katerina; Sorenson, Wendy R; Hajslova, Jana

2015-01-01

A collaborative study was conducted to determine selected polycyclic aromatic hydrocarbons (PAHs) and their relevant alkyl homologs in seafood matrixes using a fast sample preparation method followed by analysis with GC/MS. The sample preparation method involves addition of (13)C-PAH surrogate mixture to homogenized samples and extraction by shaking with a water-ethyl acetate mixture. After phase separation induced by addition of anhydrous magnesium sulfate-sodium chloride (2 + 1, w/w) and centrifugation, an aliquot of the ethyl acetate layer is evaporated, reconstituted in hexane, and cleaned up using silica gel SPE. The analytes are eluted with hexane-dichloromethane (3 + 1, v/v), the clean extract is carefully evaporated, reconstituted in isooctane, and analyzed by GC/MS. To allow for the use of various GC/MS instruments, GC columns, silica SPE cartridges, and evaporation techniques and equipment, performance-based criteria were developed and implemented in the qualification phase of the collaborative study. These criteria helped laboratories optimize their GC/MS, SPE cleanup, and evaporation conditions; check and eliminate potential PAH contamination in their reagent blanks; and become familiar with the method procedure. Ten laboratories from five countries qualified and completed the collaborative study, which was conducted on three seafood matrixes (mussel, oyster, and shrimp) fortified with 19 selected PAH analytes at five different levels of benzo[a]pyrene (BaP) ranging from 2 to 50 μg/kg. Each matrix had a varying mixture of three different BaP levels. The other studied PAHs were at varying levels from 2 to 250 μg/kg to mimic typical PAH patterns. The fortified analytes in three matrixes were analyzed as blind duplicates at each level of BaP and corresponding other PAH levels. In addition, a blank with no added PAHs for each matrix was analyzed singly. Eight to 10 valid results were obtained for the majority of determinations. Mean recoveries of all

Fast analysis of 29 polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs with ultra-high performance liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry

PubMed Central

Lung, Shih-Chun Candice; Liu, Chun-Hu

2015-01-01

Polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs are ubiquitous in the environment. Some of them are probable carcinogens and some are source markers. This work presents an ultra-high performance liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry (UHPLC-APPI-MS/MS) method for simultaneous analysis of 20 PAHs and nine nitro-PAHs. These compounds are separated in 15 minutes in the positive mode and 11 minutes in the negative mode, one half of GC/MS analysis time. Two pairs of precursor/product ions are offered, which is essential for confirmation. This method separates and quantifies benzo[a]pyrene (the most toxic PAHs) and non-priority benzo[e]pyrene (isomers, little toxicity) to avoid overestimation of toxin levels, demonstrating its importance for health-related researches. With 0.5% 2,4-difluoroanisole in chlorobenzene as the dopant, limits of detection of PAHs except acenaphthylene and those of nitro-PAHs except 2-nitrofluoranthene are below 10 pg and 3 pg, respectively, mostly lower than or comparable to those reported using LC-related systems. The responses were linear over two orders of magnitude with fairly good accuracy and precision. Certified reference materials and real aerosol samples were analyzed to demonstrate its applicability. This fast, sensitive, and reliable method is the first UHPLC-APPI-MS/MS method capable of simultaneously analyzing 29 environmentally and toxicologically important PAHs and nitro-PAHs. PMID:26265155

Degradation of polycyclic aromatic hydrocarbons (PAHs) by a mixed culture and its component pure cultures, obtained from PAH-contaminated soil.

PubMed

Trzesicka-Mlynarz, D; Ward, O P

1995-06-01

A mixed culture, isolated from soil contaminated with polycyclic aromatic hydrocarbons (PAHs), grew on and degraded fluoranthene in aqueous media supplemented with glucose, yeast extract, and peptone. Increased complex nitrogen levels in the medium promoted bacterial growth and a greater extent of fluoranthene degradation. Amendment of the media with high glucose levels also diminished specific fluoranthene degradation. The mixed culture was capable of degrading a range of other PAHs, including benzo[a]pyrene, anthracene, phenanthrene, acenaphthene, and fluorene. The mixed culture contained four predominant isolates, all of which were Gram-negative rods, three of which were identified as Pseudomonas putida, Flavobacterium sp., and Pseudomonas aeruginosa. Better degradation of a defined PAH mixture was observed with the mixed culture than with individual isolates. A reconstituted culture, prepared by combining the four individual isolates, manifested a similar PAH biodegradation performance to the original mixed culture. When compared with the mixed culture, individual isolates exhibited a relatively good capacity to remove more water-soluble PAHs (acenaphthene, fluorene, phenanthrene, fluoranthene). In contrast, removal of less water-soluble PAHs (anthracene and pyrene) was low or negligible with isolated cultures compared with the mixed culture.

PAH Formation in O-rich Evolved Stars

NASA Astrophysics Data System (ADS)

Guzman-Ramirez, L.; Lagadec, E.; Jones, D.; Zijlstra, A. A.; Gesicki, K.

2015-08-01

Polycyclic aromatic hydrocarbons (PAHs) have been observed in O-rich planetary nebulae. This combination of oxygen-rich and carbon-rich material, known as dual-dust or mixed chemistry, is not expected to be seen around these objects. We recently proposed that PAHs could be formed from the photodissociation of CO in dense tori. Using VISIR/VLT, we spatially resolved the emission of the PAH bands and ionised emission from the [S IV] line, confirming the presence of dense central tori in all the observed O-rich objects. Furthermore, we show that for most of the objects, PAHs are located at the outer edge of these dense/compact tori, while the ionised material is mostly present in the inner parts, consistent with our hypothesis for the formation of PAHs in these systems. The presence of a dense torus has been strongly associated with the action of a central binary star and, as such, the rich chemistry seen in these regions may also be related to the formation of exoplanets in post-common-envelope binary systems.

Quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair by HPLC with fluorescence detection: a biological monitoring method to evaluate the exposure to PAHs.

PubMed

Toriba, Akira; Kuramae, Yayoi; Chetiyanukornkul, Thaneeya; Kizu, Ryoichi; Makino, Tsunehisa; Nakazawa, Hiroyuki; Hayakawa, Kazuichi

2003-01-01

A high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair. Fifteen kinds of PAHs classified as priority pollutants by the US EPA were quantified with four perdeuterated PAHs as internal standards. After 50 mg hair samples were washed with n-hexane to remove external contamination of PAHs, the samples were digested in 2.5 M sodium hydroxide. The digests were extracted with n-hexane and then analyzed by HPLC. Eleven kinds of PAHs were identified in hair samples of 20 subjects, and 10 kinds of PAHs were eventually quantified using the internal standards. For anthracene, chrysene and benzo[k]fluoranthene, significant differences were observed between smokers and non-smokers. Although benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were observed in the particulates of indoor and outdoor air, they were not detected in all hair samples. The analysis of PAHs in human hair should be useful as a new biomarker to evaluate the exposure to PAHs.

PAH volatilization following application of coal-tar-based pavement sealant

USGS Publications Warehouse

Van Metre, Peter C.; Majewski, Michael S.; Mahler, Barbara J.; Foreman, William T.; Braun, Christopher L.; Wilson, Jennifer T.; Burbank, Teresa L.

2012-01-01

Coal-tar-based pavement sealants, a major source of PAHs to urban water bodies, have recently been identified as a source of volatile PAHs to the atmosphere. We tracked the volatilization of PAHs for 1 year after application of a coal-tar-based pavement sealant by measuring gas-phase PAH concentrations above the pavement surface and solid-phase PAH concentrations in sealant scraped from the surface. Gas-phase concentrations at two heights (0.03 and 1.28 m) and wind speed were used to estimate volatilization flux. The sum of the concentrations of eight frequently detected PAHs (ΣPAH8) in the 0.03-m sample 1.6 h after application (297,000 ng m-3) was about 5000 times greater than that previously reported for the same height above unsealed parking lots (66 ng m-3). Flux at 1.6 h after application was estimated at 45,000 μg m-2 h-1 and decreased rapidly during the 45 days after application to 160 μg m-2 h-1. Loss of PAHs from the adhered sealant also was rapid, with about a 50% decrease in solid-phase ΣPAH8 concentration over the 45 days after application. There was general agreement, given the uncertainties, in the estimated mass of ΣPAH8 lost to the atmosphere on the basis of air sampling (2–3 g m-2) and adhered sealant sampling (6 g m-2) during the first 16 days after application, translating to a loss to the atmosphere of one-quarter to one-half of the PAHs in the sealcoat product. Combining the estimated mass of ΣPAH8 released to the atmosphere with a national-use estimate of coal-tar-based sealant suggests that PAH emissions from new coal-tar-based sealcoat applications each year (~1000 Mg) are larger than annual vehicle emissions of PAHs for the United States.

Decontamination of soils containing PAHs by electroremediation: a review.

PubMed

Pazos, M; Rosales, E; Alcántara, T; Gómez, J; Sanromán, M A

2010-05-15

During the last years, the anthropogenic sources have contributed to organic compound penetration into the environment. One large group of persistent and toxic contaminants is the hydrophobic organic contaminants. Among them, polycyclic aromatic hydrocarbons (PAHs) have been recognized as a representative group of these pollutants with low solubility. In this paper, it is showed the electroremediation of soil contaminated with PAHs as an alternative, to organic compound removal. This technique, mainly used for heavy metal extraction, applies the electric current to promote the movement of contaminants. Nowadays the application of this technique alone or combined with other techniques as for example Fenton or bioremediation is taking fine results to PAHs removal. Although the PAHs soil decontamination by means of the electric field is in an initial stage, many researchers have demonstrated the treatment effectiveness. This paper describes the foremost principles to carry out the electroremediation of soils contaminated with PAHs, just like the different alternatives to improve the electroremediation of PAHs and also the new methodologies of PAHs removal by using hybrid technologies. Copyright (c) 2009 Elsevier B.V. All rights reserved.

PAH emissions from coal combustion and waste incineration.

PubMed

Hsu, Wei Ting; Liu, Mei Chen; Hung, Pao Chen; Chang, Shu Hao; Chang, Moo Been

2016-11-15

The characteristics of PAHs that are emitted by a municipal waste incinerator (MWI) and coal-fired power plant are examined via intensive sampling. Results of flue gas sampling reveal the potential for PAH formation within the selective catalytic reduction (SCR) system of a coal-fired power plant. In the large-scale MWI, the removal efficiency of PAHs achieved with the pilot-scaled catalytic filter (CF) exceeds that achieved by activated carbon injection with a bag filter (ACI+BF) owing to the effective destruction of gas-phase contaminants by a catalyst. A significantly lower PAH concentration (1640ng/g) was measured in fly ash from a CF module than from an ACI+BF system (5650ng/g). Replacing the ACI+BF system with CF technology would significantly reduce the discharge factor (including emission and fly ash) of PAHs from 251.6 to 77.8mg/ton-waste. The emission factors of PAHs that are obtained using ACI+BF and the CF system in the MWI are 8.05 and 7.13mg/ton, respectively. However, the emission factor of MWI is significantly higher than that of coal-fired power plant (1.56mg/ton). From the perspective of total environmental management to reduce PAH emissions, replacing the original ACI+BF process with a CF system is expected to reduce environmental impact thereof. Copyright © 2016 Elsevier B.V. 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

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

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

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

1994-12-31

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

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.

Phytoavailability and mechanism of bound PAH residues in filed contaminated soils.

PubMed

Gao, Yanzheng; Hu, Xiaojie; Zhou, Ziyuan; Zhang, Wei; Wang, Yize; Sun, Bingqing

2017-03-01

Understanding the phytoavailability of bound residues of polycyclic aromatic hydrocarbons (PAHs) in soils is essential to assessing their environmental fate and risks. This study investigated the release and plant uptake of bound PAH residues (reference to parent compounds) in field contaminated soils after the removal of extractable PAH fractions. Plant pot experiments were performed in a greenhouse using ryegrass (Lolium multiflorum Lam.) to examine the phytoavailablility of bound PAH residues, and microcosm incubation experiments with and without the addition of artificial root exudates (AREs) or oxalic acid were conducted to examine the effect of root exudates on the release of bound PAH residues. PAH accumulation in the ryegrass after a 50-day growth period indicated that bound PAH residues were significantly phytoavailable. The extractable fractions, including the desorbing and non-desorbing fractions, dominated the total PAH concentrations in vegetated soils after 50 days, indicating the transfer of bound PAH residues to the extractable fractions. This transfer was facilitated by root exudates. The addition of AREs and oxalic acid to test soils enhanced the release of bound PAH residues into their extractable fractions, resulting in enhanced phytoavailability of bound PAH residues in soils. This study provided important information regarding environmental fate and risks of bound PAH residues in soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Predicting the diurnal blue-sky albedo of soils using their laboratory reflectance spectra and roughness indices

NASA Astrophysics Data System (ADS)

Cierniewski, Jerzy; Ceglarek, Jakub; Karnieli, Arnon; Królewicz, Sławomir; Kaźmierowski, Cezary; Zagajewski, Bogdan

2017-10-01

The objective of this study was to assess the relationship between the hyperspectral reflectance of soils and their albedo, measured under various roughness conditions. 108 soil surface measurements were conducted in Poland and Israel. Each surface was characterised by its diurnal albedo variation in the field as well as by its reflectance spectra obtained in the laboratory. The best fit to the model was achieved by post-processing manipulation of the spectra, namely second derivate transformation. Using a stepwise elimination process, four spectral wavelengths and the roughness index were selected for modelling. The resulting models allowed the albedo of a soil to be predicted for its different roughness states and any solar zenith angle, provided that hyperspectral reflectance data is available.

Environmental and individual PAH exposures near rural natural gas extraction.

PubMed

Paulik, L Blair; Hobbie, Kevin A; Rohlman, Diana; Smith, Brian W; Scott, Richard P; Kincl, Laurel; Haynes, Erin N; Anderson, Kim A

2018-05-29

Natural gas extraction (NGE) has expanded rapidly in the United States in recent years. Despite concerns, there is little information about the effects of NGE on air quality or personal exposures of people living or working nearby. Recent research suggests NGE emits polycyclic aromatic hydrocarbons (PAHs) into air. This study used low-density polyethylene passive samplers to measure concentrations of PAHs in air near active (n = 3) and proposed (n = 2) NGE sites. At each site, two concentric rings of air samplers were placed around the active or proposed well pad location. Silicone wristbands were used to assess personal PAH exposures of participants (n = 19) living or working near the sampling sites. All samples were analyzed for 62 PAHs using GC-MS/MS, and point sources were estimated using the fluoranthene/pyrene isomer ratio. ∑PAH was significantly higher in air at active NGE sites (Wilcoxon rank sum test, p < 0.01). PAHs in air were also more petrogenic (petroleum-derived) at active NGE sites. This suggests that PAH mixtures at active NGE sites may have been affected by direct emissions from petroleum sources at these sites. ∑PAH was also significantly higher in wristbands from participants who had active NGE wells on their properties than from participants who did not (Wilcoxon rank sum test, p < 0.005). There was a significant positive correlation between ∑PAH in participants' wristbands and ∑PAH in air measured closest to participants' homes or workplaces (simple linear regression, p < 0.0001). These findings suggest that living or working near an active NGE well may increase personal PAH exposure. This work also supports the utility of the silicone wristband to assess personal PAH exposure. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

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

Hudson, R. L.; Loeffler, M. J.; Yocum, K. M., E-mail: Reggie.Hudson@nasa.gov

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal andmore » acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.« less

[Comparison of polycyclic aromatic hydrocarbons (PAHS) contents in bakery products].

PubMed

Ciemniak, Artur; Witczak, Agata

2010-01-01

Polycyclic aromatic hydrocarbons are a group of well-known chemical carcinogens with a wide distribution in the environment and formed by the incomplete combustion of organic substances. PAHs have attracted most attention because of their carcinogenic potential. PAHs have been found as contaminants in different food categories such as dairy products, smoked and barbecued meat, vegetables, fruits, oils, coffee, tea, and cereals. Processing of food at high temperatures increases the amount of PAHs in the food Diet is the major source of human exposure to PAHs. The major dietary source of PAH are oils and fats, cereals products and vegetables. The aims of this study were to determine the content levels of 23 PAHs in various sorts of bread. The analytical procedure was based Soxhlet extraction with n--hexane and cleaned up in aflorisil cartridge. Chromatographic separation was performed using gas chromatography (HP 6890) coupled to mass spectrometry (HP 5973). The total concentration of PAHs was low end varied between 2.61 microg/kg to 43.4 microg/kg. Furthermore, the results revealed differences in concentrations of PAHs between rind and bread-crumb.

Gas chromatographic retention behavior of polycyclic aromatic hydrocarbons (PAHs) and alkyl-substituted PAHs on two stationary phases of different selectivity.

PubMed

Nalin, Federica; Sander, Lane C; Wilson, Walter B; Wise, Stephen A

2018-01-01

Retention indices (I) for 45 polycyclic aromatic hydrocarbons (PAHs) and 63 methyl-substituted PAHs were determined by gas chromatography - mass spectrometry (GC-MS) using two different stationary phases: a Rxi-PAH phase (a "higher phenyl-content stationary phase") and a 50% (mole fraction) liquid crystalline dimethylpolysiloxane phase. Retention data were obtained for parent PAHs from molecular mass (MM) 128 g/mol (naphthalene) to 328 g/mol (benzo[c]picene) and for 12 sets of methyl-PAHs (methylfluorenes, methylanthracenes, methylphenanthrenes, methylfluoranthenes, methylpyrenes, methylbenz[a]anthracenes, methylbenzo[c]phenanthrenes, methylchrysenes, methyltriphenylenes, methylbenzo[a]pyrenes, methylperylenes, and methylpicenes). Molecular shape descriptors such as length-to-breath ratio (L/B) and thickness (T) were determined for all the PAHs studied. Correlation between I and L/B ratio was evaluated for both stationary phases with a better correlation observed for the 50% liquid crystalline phase (correlation coefficients ranging from 0.22 to 1.00). Graphical Abstract GC separation of six methylchrysene isomers (m/z 242) on two different stationary phases: 50 % phenyl-like methylpolysiloxane phase and 50 % liquid crystalline phase. Retention indices (I) are plotted as a function of L/B for both phases. The data marker numbers identify each isomer based on methyl-substitution position.

PAH and OPAH Flux during the Deepwater Horizon Incident

PubMed Central

Tidwell, Lane G.; Allan, Sarah E.; O'Connell, Steven G.; Hobbie, Kevin A.; Smith, Brian W.; Anderson, Kim A.

2016-01-01

Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water-air boundary was determined. This is the first report of vapor phase and diffusive flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 6.6 and 210 ng/m3 and 0.02 and 34 ng/m3 respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air-water flux of 13 individual PAHs was shown to be at least partially influenced by the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi at nominal rates of 56,000 and 42,000 ng/m2/day in the summer. Naphthalene was the PAH with the highest observed volatilization rate of 52,000 ng/m2/day in June 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air-water chemical flux determinations with passive sampling technology. PMID:27391856

Ejecta patterns of Meteor Crater, Arizona derived from the linear un-mixing of TIMS data and laboratory thermal emission spectra

NASA Technical Reports Server (NTRS)

Ramsey, Michael S.; Christensen, Philip R.

1992-01-01

Accurate interpretation of thermal infrared data depends upon the understanding and removal of complicating effects. These effects may include physical mixing of various mineralogies and particle sizes, atmospheric absorption and emission, surficial coatings, geometry effects, and differential surface temperatures. The focus is the examination of the linear spectral mixing of individual mineral or endmember spectra. Linear addition of spectra, for particles larger than the wavelength, allows for a straight-forward method of deconvolving the observed spectra, predicting a volume percent of each endmember. The 'forward analysis' of linear mixing (comparing the spectra of physical mixtures to numerical mixtures) has received much attention. The reverse approach of un-mixing thermal emission spectra was examined with remotely sensed data, but no laboratory verification exists. Understanding of the effects of spectral mixing on high resolution laboratory spectra allows for the extrapolation to lower resolution, and often more complicated, remotely gathered data. Thermal Infrared Multispectral Scanner (TIMS) data for Meteor Crater, Arizona were acquired in Sep. 1987. The spectral un-mixing of these data gives a unique test of the laboratory results. Meteor Crater (1.2 km in diameter and 180 m deep) is located in north-central Arizona, west of Canyon Diablo. The arid environment, paucity of vegetation, and low relief make the region ideal for remote data acquisition. Within the horizontal sedimentary sequence that forms the upper Colorado Plateau, the oldest unit sampled by the impact crater was the Permian Coconino Sandstone. A thin bed of the Toroweap Formation, also of Permian age, conformably overlays the Coconino. Above the Toroweap lies the Permian Kiabab Limestone which, in turn, is covered by a thin veneer of the Moenkopi Formation. The Moenkopi is Triassic in age and has two distinct sub-units in the vicinity of the crater. The lower Wupatki member is a fine

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.

Comparative Developmental Toxicity of Environmentally Relevant Oxygenated PAHs

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

Knecht, Andrea; Goodale, Britton; Truong, Lisa

2013-09-01

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in urban air, dust and in the soil of most industrial coal gassification, coal burning, coke production and wood preservation sites (Howsam and Jones 1998). It is widely recognized that PAHs pose risks to human health,having been associated with increased risks of systemic inflammation (Delfino et al. 2010), cardiopulmonary mortality (Lee et al. 2011; Lewtas 2007) and lung cancer mortality (Grant 2009; Hoshuyama et al. 2006). The potential risks may be especially acute for the developing fetus and infant where PAH exposures have been linked to low birth weight, intrauterine growth retardation, in-uteromore » mortality and lower intelligence (Dejmek et al. 1999; Dejmek et al. 2000; Perera et al. 1999; Perera et al. 2009; Perera et al. 2006; Perera et al. 1998; Wu et al. 2010). Despite the more than two decades of intensive study devoted to parent PAHs, they are only part of the hazard spectrum from PAH contamination.« less

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

NASA Astrophysics Data System (ADS)

Bejaoui, Salma; Salama, Farid

2015-08-01

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

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.

Water-Sediment Partition of Polycyclic Aromatic Hydrocarbons (PAHs) in Nansi Lake

NASA Astrophysics Data System (ADS)

Zhang, Guizhai; Diao, Youjiang

2018-06-01

Based on field data of polycyclic aromatic hydrocarbons (PAHs) in water and sediment in Nansi Lake. The concentrations and the partitioning characteristic of PAHs in the water and sediment were studied. The lgKd of high molecular weight PAHs were higher than the low molecular weight PAHs. The most of PAHs Kd values were negligible correlated with TOC, soluble salt, clay and pH of the sediment in Nansi Lake.

Composition and Integrity of PAHs, Nitro-PAHs, Hopanes and Steranes In Diesel Exhaust Particulate Matter.

PubMed

Huang, Lei; Bohac, Stanislav V; Chernyak, Sergei M; Batterman, Stuart A

2013-08-01

Diesel exhaust particulate matter contains many semivolatile organic compounds (SVOCs) of environmental and health significance. This study investigates the composition, emission rates, and integrity of 25 SVOCs, including polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and diesel biomarkers hopanes and steranes. Diesel engine particulate matter (PM), generated using an engine test bench, three engine conditions, and ultra-low sulfur diesel (ULSD), was collected on borosilicate glass fiber filters. Under high engine load, the PM emission rate was 0.102 g/kWh, and emission rate of ΣPAHs (10 compounds), ΣNPAHs (6 compounds), Σhopanes (2 compounds), and Σsteranes (2 compounds) were 2.52, 0.351, 0.02 ~ 2 and 1μg/kWh, respectively. Storage losses were evaluated for three cases: conditioning filters in clean air at 25 °C and 33% relative humidity (RH) for 24 h; storing filter samples (without extraction) wrapped in aluminum foil at 4 °C for up to one month; and storing filter extracts in glass vials capped with Teflon crimp seals at 4 °C for up to six months. After conditioning filters for 24 h, 30% of the more volatile PAHs were lost, but lower volatility NPAHs, hopanes and steranes showed negligible changes. Storing wrapped filters and extracts at 4 °C for up to one month did not lead to significant losses, but storing extracts for five months led to significant losses of PAHs and NPAHs; hopanes and steranes demonstrated greater integrity. These results suggest that even relatively brief filter conditioning periods, needed for gravimetric measurements of PM mass, and extended storage of filter extracts can lead to underestimates of SVOC concentrations. Thus, SVOC sampling and analysis protocols should utilize stringent criteria and performance checks to identify and limit possible biases occurring during filter and extract processing.

Composition and Integrity of PAHs, Nitro-PAHs, Hopanes and Steranes In Diesel Exhaust Particulate Matter

PubMed Central

Huang, Lei; Bohac, Stanislav V.; Chernyak, Sergei M.; Batterman, Stuart A.

2013-01-01

Diesel exhaust particulate matter contains many semivolatile organic compounds (SVOCs) of environmental and health significance. This study investigates the composition, emission rates, and integrity of 25 SVOCs, including polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and diesel biomarkers hopanes and steranes. Diesel engine particulate matter (PM), generated using an engine test bench, three engine conditions, and ultra-low sulfur diesel (ULSD), was collected on borosilicate glass fiber filters. Under high engine load, the PM emission rate was 0.102 g/kWh, and emission rate of ΣPAHs (10 compounds), ΣNPAHs (6 compounds), Σhopanes (2 compounds), and Σsteranes (2 compounds) were 2.52, 0.351, 0.02 ~ 2 and 1μg/kWh, respectively. Storage losses were evaluated for three cases: conditioning filters in clean air at 25 °C and 33% relative humidity (RH) for 24 h; storing filter samples (without extraction) wrapped in aluminum foil at 4 °C for up to one month; and storing filter extracts in glass vials capped with Teflon crimp seals at 4 °C for up to six months. After conditioning filters for 24 h, 30% of the more volatile PAHs were lost, but lower volatility NPAHs, hopanes and steranes showed negligible changes. Storing wrapped filters and extracts at 4 °C for up to one month did not lead to significant losses, but storing extracts for five months led to significant losses of PAHs and NPAHs; hopanes and steranes demonstrated greater integrity. These results suggest that even relatively brief filter conditioning periods, needed for gravimetric measurements of PM mass, and extended storage of filter extracts can lead to underestimates of SVOC concentrations. Thus, SVOC sampling and analysis protocols should utilize stringent criteria and performance checks to identify and limit possible biases occurring during filter and extract processing. PMID:24363468

Cloud deposition of PAHs at Mount Lushan in southern China.

PubMed

Wang, Ruixia; Wang, Yan; Li, Hongli; Yang, Minmin; Sun, Lei; Wang, Tao; Wang, Wenxing

2015-09-01

Cloud water samples were collected from Mount Lushan, a high alpine area of southern China, and analyzed using GC-MS to investigate the concentration levels, seasonal variations, particle-dissolved phase partitioning, ecological risk of PAHs and its relationship to the atmosphere and rainwater. The average concentration of total (dissolved+particle) PAHs in cloud water was 819.90 ng/L, which ranged from 2.30 ng/L for DbA to 295.38 ng/L for PhA. PhA (33.11%) contributed the most individual PAHs, followed by Flu (28.24%). Distinct seasonal variations in the total PAHs measured in this research had a higher concentration during the spring and a lower concentration during the summer. When cloud events occurred, the concentration of the atmospheric PAHs of the two phases decreased. The contribution from the gaseous phase of total PAHs in the air to the dissolved phase in cloud water was up to 60.43%, but the particulate phase in the air only contributed 39.57% to the total scavenging. The contribution of total PAHs from the atmosphere to clouds is higher in the gaseous phase than in the particulate phase. A comparative study of the concentrations of cloud water and the closest rain water revealed that the PAH concentration in rainwater was 1.80 times less than that of cloud water and that the dominant individual compounds in cloud water and rainwater were PhA and Flu. A total of 81.27% of the PAHs in cloud samples and 72.21% of the PAHs in rain samples remained in the dissolved phase. Ecological risk assessment indicated that PAHs in cloud water in spring and summer caused a certain degree of ecosystem risk and the mean ecosystem risk in spring was higher than that in summer. Copyright © 2015 Elsevier B.V. All rights reserved.

Grafted cellulose for PAHs removal present in industrial discharge waters

NASA Astrophysics Data System (ADS)

Euvrard, Elise; Druart, Coline; Poupeney, Amandine; Crini, Nadia; Vismara, Elena; Lanza, Tommaso; Torri, Giangiacomo; Gavoille, Sophie; Crini, Gregorio

2014-05-01

Keywords: cellulose; biosorbent; PAHs; polycontaminated wastewaters; trace levels. Polycyclic aromatic hydrocarbons (PAHs), chemicals essentially formed during incomplete combustion of organic materials from anthropogenic activities, were present in all compartments of the ecosystem, air, water and soil. Notably, a part of PAHs found in aquatic system was introduced through industrial discharge waters. Since the Water Framework Directive has classified certain PAHs as priority hazardous substances, industrials are called to take account this kind of organic pollutants in their global environmental concern. Conventional materials such as activated carbons definitively proved their worth as finishing treatment systems but remained costly. In this study, we proposed to use cellulose grafted with glycidyl methacrylate [1] for the removal of PAHs present in discharge waters of surface treatment industries. Firstly, to develop the device, we worked with synthetic solutions containing 16 PAHs at 500 ng/L. Two types of grafted cellulose were tested over a closed-loop column with a concentration of 4g cellulose/L: cellulose C2 with a hydroxide group and cellulose C4 with an amine group. No PAH was retained by the raw cellulose whereas abatement percentages of PAHs were similar between C2 and C4 (94% and 98%, respectively, for the sum of the 16 PAHs) with an experiment duration of 400 min (corresponding to about 20 cycles through grafted cellulose). Secondly, to determine the shorter time to abate the amount maximum of PAHs through the system, a kinetic was realized from 20 min (one cycle) to 400 min with C4. The steady state (corresponding to about 95% of abatement of the total PAHs) was reached at 160 min. Finally, the system was then tested with real industrial discharge waters containing both mineral and organic compounds. The results indicated that the abatement percentage of PAHs was similar between C2 and C4, corroborating the tests with synthetic solution. In return

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.

Polycyclic aromatic hydrocarbons (PAHs) from coal combustion: emissions, analysis, and toxicology.

PubMed

Liu, Guijian; Niu, Zhiyuan; Van Niekerk, Daniel; Xue, Jian; Zheng, Liugen

2008-01-01

Coal may become more important as an energy source in the 21st century, and coal contains large quantities of organic and inorganic matter. When coal burns chemical and physical changes take place, and many toxic compounds are formed and emitted. Polycyclic aromatic hydrocarbons (PAHs) are among those compounds formed and are considered to pose potential health hazards because some PAHs are known carcinogens. Based on their toxicology, 16 PAHs are considered as priority pollutants by the USEPA. More attention must be given to the various methods of extraction and analysis of PAH from coal or coal products to accurately explain and determine the species of PAHs. The influences of the extraction time, solvents, and methods for PAH identification are important. In the future, more methods and influences will be studied more carefully and widely. PAHs are environmental pollutants, are highly lipid soluble, and can be absorbed by the lungs, gut, and skin of mammals because they are associated with fine particles from coal combustion. More attention is being given to PAHs because of their carcinogenic and mutagenic action. We suggest that when using a coal stove indoors, a chimney should be used; the particles and gas containing PAHs should be released outdoors to reduce the health hazard, especially in Southwest China. During coal utilization processes, such as coal combustion and pyrolysis, PAHs released may be divided into two categories according to their formation pathways: one pathway is derived from complex chemical reactions and the other is from free PAHs transferred from the original coal. The formation and emission of PAHs is a complex physical and chemical process that has received considerable attention in recent years. It is suggested that the formation mechanisms of PAHs will be an increasingly important topic for researchers to find methods for controlling emissions during coal combustion.

Ability of natural attenuation and phytoremediation using maize (Zea mays L.) to decrease soil contents of polycyclic aromatic hydrocarbons (PAHs) derived from biomass fly ash in comparison with PAHs-spiked soil.

PubMed

Košnář, Zdeněk; Mercl, Filip; Tlustoš, Pavel

2018-05-30

A 120-day pot experiment was conducted to compare the ability of natural attenuation and phytoremediation approaches to remove polycyclic aromatic hydrocarbons (PAHs) from soil amended with PAHs-contaminated biomass fly ash. The PAH removal from ash-treated soil was compared with PAHs-spiked soil. The removal of 16 individual PAHs from soil ranged between 4.8% and 87.8% within the experiment. The natural attenuation approach led to a negligible total PAH removal. The phytoremediation was the most efficient approach for PAH removal, while the highest removal was observed in the case of ash-treated soil. The content of low molecular weight (LMW) PAHs and the total PAHs in this treatment significantly decreased (P <.05) over the whole experiment by 47.6% and 29.4%, respectively. The tested level of PAH soil contamination (~1600 µg PAH/kg soil dry weight) had no adverse effects on maize growth as well on the biomass yield. In addition, the PAHs were detected only in maize roots and their bioaccumulation factors were significantly lower than 1 suggesting negligible PAH uptake from soil by maize roots. The results showed that PAHs of ash origin were similarly susceptible to removal as spiked PAHs. The presence of maize significantly boosted the PAH removal from soil and its aboveground biomass did not represent any environmental risk. Copyright © 2018 Elsevier Inc. All rights reserved.

The Occurrence of 16 EPA PAHs in Food – A Review

PubMed Central

Zelinkova, Zuzana; Wenzl, Thomas

2015-01-01

Occurrence and toxicity of polycyclic aromatic hydrocarbons (PAHs) have been extensively studied in countries all over the world. PAHs generally occur in complex mixtures which may consist of hundreds of compounds. The U.S. Environmental Protection Agency (EPA) proposed in the 1970 to monitor a set of 16 PAHs which are frequently found in environmental samples. This article reviews the suitability of the 16 EPA PAHs for the assessment of potential health threats to humans stemming from the exposure to PAHs by food ingestion. It presents details on analysis methods, the occurrence of PAHs in food, regulatory aspects, and related risk management approaches. In addition, consideration is given to newer evaluations of the toxicity of PAHs and the requirements for risk assessment and management stemming from them. PMID:26681897

The Spitzer Atlas of Stellar Spectra (SASS)

NASA Astrophysics Data System (ADS)

Ardila, D. R.; van Dyk, S. D., Makowiecki, W.; Stauffer, J.; Song, I.; Ro, J.; Fajardo-Acosta, S.; Hoard, D. W.; Wachter, S.

2011-11-01

We present the Spitzer Atlas of Stellar Spectra (SASS), which includes 159 stellar spectra (5 to 32 micron; R about 100) taken with the Infrared Spectrograph on the Spitzer Space Telescope. This Atlas gathers representative spectra of a broad section of the Hertzsprung-Russell diagram, intended to serve as a general stellar spectral reference in the mid-infrared. It includes stars from all luminosity classes, as well as Wolf-Rayet (WR) objects. Furthermore, it includes some objects of intrinsic interest, like blue stragglers and certain pulsating variables. All the spectra have been uniformly reduced, and all are available online. For dwarfs and giants, the spectra of early-type objects are relatively featureless, dominated by Hydrogen lines around A spectral types. Besides these, the most noticeable photospheric features correspond to water vapor and silicon monoxide in late-type objects and methane and ammonia features at the latest spectral types. Most supergiant spectra in the Atlas present evidence of circumstellar gas. The sample includes five M supergiant spectra, which show strong dust excesses and in some cases PAH features. Sequences of WR stars present the well-known pattern of lines of He I and He II, as well as forbidden lines of ionized metals. The characteristic flat-top shape of the [Ne III] line is evident even at these low spectral resolutions. Several Luminous Blue Variables and other transition stars are present in the Atlas and show very diverse spectra, dominated by circumstellar gas and dust features. We show that the [8]-[24] Spitzer colors (IRAC and MIPS) are poor predictors of spectral type for most luminosity classes.

Solubilization, Solution Equilibria, and Biodegradation of PAH's under Thermophilic Conditions

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

Viamajala, S.; Peyton, B. M.; Richards, L. A.

Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 C, 40 C and 60 C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energymore » of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.« less

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.

Are urinary PAHs biomarkers of controlled exposure to diesel exhaust?

PubMed Central

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

2016-01-01

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

PAH Emission in the Orion Bar

NASA Technical Reports Server (NTRS)

Bregman, Jesse; Sloan, G. C.

1996-01-01

The emission from polycyclic aromatic hydrocarbons (PAH's) in the Orion Bar region is investigated using a combination of narrow-band imaging and long-slit spectroscopy. The goal was to study how the strength of the PAH bands vary with spatial position in this edge-on photo-dissociation region. The specific focus here is how these variations constrain the carrier of the 3.4 micron band.

Surface water polycyclic aromatic hydrocarbons (PAH) in urban areas of Nanjing, China.

PubMed

Wang, Chunhui; Zhou, Shenglu; Wu, Shaohua; Song, Jing; Shi, Yaxing; Li, Baojie; Chen, Hao

2017-10-01

The concentration, sources and environmental risks of polycyclic aromatic hydrocarbons (PAHs) in surface water in urban areas of Nanjing were investigated. The range of ∑ 16 PAHs concentration is between 4,076 and 29,455 ng/L, with a mean of 17,212 ng/L. The composition of PAHs indicated that 2- and 3-ring PAHs have the highest proportion in all PAHs, while the 5- and 6-ring PAHs were the least in proportion. By diagnostic ratio analysis, combustion and petroleum were a mixture input that contributed to the water PAH in urban areas of Nanjing. Positive matrix factorization quantitatively identified four factors, including coke oven, coal combustion, oil source, and vehicle emission, as the main sources. Toxic equivalency factors of BaP (BaP eq ) evaluate the environmental risks of PAHs and indicate the PAH concentration in surface water in urban areas of Nanjing had been polluted and might cause potential environmental risks. Therefore, the PAH contamination in surface water in urban areas of Nanjing should draw considerable attention.

Biochar accelerates PAHs biodegradation in petroleum-polluted soil by biostimulation strategy.

PubMed

Kong, Lulu; Gao, Yuanyuan; Zhou, Qixing; Zhao, Xuyang; Sun, Zhongwei

2018-02-05

Sawdust and wheat straw biochars prepared at 300°C and 500°C were applied to petroleum-polluted soil for an 84-day incubation to estimate their effectiveness on polycyclic aromatic hydrocarbons (PAHs) removal. Biochars alone were most effective at reducing PAHs contents. However, adding biochar to soils in company with NaN 3 solution resulted in a decreasing trend in terms of PAHs removal, which was even lower than treatment CK without biochar. Moreover, it was discovered by PCR-DGGE files and sequencing analysis that the predominant bacterial diversity slightly decreased but the abundance of some specific taxa, including PAHs degraders, was promoted with biochar input. These results highlighted the potential of biochar application on accelerating PAHs biodegradation, which could be attributed to the properties of biochars that benefit for making the amended soil a better habitat for microbes. The impacts of biochar preparation and pollutants nature on PAHs removal were also determined. Significant reduction in the PAHs contents was detected when adding biochar prepared at a high temperature (500°C), while the feedstocks of biochar showed little effect on PAHs removal. Due to the high hydrophobicity of aromatic rings, high-molecular weight PAHs were found much more resistant to microbial degradation in comparison with low-molecular weight PAHs. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Environmental distribution of PAHs in pine needles, soils, and sediments.

PubMed

Navarro-Ortega, Alícia; Ratola, Nuno; Hildebrandt, Alain; Alves, Arminda; Lacorte, Sílvia; Barceló, Damià

2012-03-01

The content of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in 60 samples from three environmental matrices (soils, sediments, and pine needles) in an effort to assess their distribution on a river basin scale. A sampling campaign was carried out in 2006, selecting urban, industrial, and agricultural sampling sites along the northeast of Spain. Techniques used included pressurized liquid extraction and solid-liquid ultrasonic extraction followed by gas chromatography-electron impact ionization mass spectrometry. The mean total PAHs concentrations were 290 < 613 < 1,628 ng/g (dry weight) in pine needles, soil, and sediments, respectively. There is a good correspondence between the total concentration of soils and pine needles, as opposed to the levels between sediments and pine needles. The high concentrations found in some Pinus halepensis samples may reflect a superior uptake potential of this species in comparison to the others studied. The three matrices present a very different PAH distribution pattern, with pine needles showing a predominance of the lighter (2-, 3-, and 4-ring) PAHs, whereas 5- and 6-ring PAHs are the most abundant in soils. Sediments display a more heterogeneous pattern, with contributions of all the PAHs but different distribution depending on the site, suggesting a wider range of input sources. Established PAH molecular ratios and principal component analysis were used to identify the origins and profiles of PAHs. While sediments showed a wide range attributed to historical inputs, soils and pine needles confirmed the compartmentalization of the PAHs, with lighter airborne PAHs accumulated in pine needles and heavier ones in soils. It can be suggested that the monitoring of several matrices is a strong tool to elucidate the contamination sources and accumulation patterns of PAHs. However, given the influence of the matrix type on this assessment, the information should be considered complementary, yet allowing a more

Comparing PAH availability from manufactured gas plant soils and sediments with chemical and biological tests. 1. PAH release during water desorption and supercritical carbon dioxide extraction.

PubMed

Hawthorne, Steven B; Poppendieck, Dustin G; Grabanski, Carol B; Loehr, Raymond C

2002-11-15

Soil and sediment samples from oil gas (OG) and coal gas (CG) manufactured gas plant (MGP) sites were selected to represent a range of PAH concentrations (150-40,000 mg/kg) and sample matrix compositions. Samples varied from vegetated soils to lampblack soot and had carbon contents from 3 to 87 wt %. SFE desorption (120 min) and water/XAD2 desorption (120 days) curves were determined and fit with a simple two-site model to determine the rapid-released fraction (F) for PAHs ranging from naphthalene to benzo[ghi]perylene. F values varied greatly among the samples, from ca. 10% to >90% for the two- and three-ring PAHs and from <1% to ca. 50% for the five- and six-ring PAHs. Release rates did not correlate with sample matrix characteristics including PAH concentrations, elemental composition (C, H, N, S), or "hard" and "softs" organic carbon, indicating that PAH release cannot easily be estimated on the basis of sample matrix composition. Fvalues for CG site samples obtained with SFE and water desorption agreed well (linear correlation coefficient, r2 = 0.87, slope = 0.93), but SFE yielded higher F values for the OG samples. These behaviors were attributed to the stronger ability of carbon dioxide than water to desorb PAHs from the highly aromatic (hard) carbon of the OG matrixes, while carbon dioxide and water showed similar abilities to desorb PAHs from the more polar (soft) carbon of the CG samples. The combined SFE and water desorption approaches should improve the understanding of PAH sequestration and release from contaminated soils and sediments and provide the basis for subsequent studies using the same samples to compare PAH release with PAH availability to earthworms.

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

Dissolved oxygen saturation controls PAH biodegradation in freshwater estuary sediments.

PubMed

Boyd, T J; Montgomery, M T; Steele, J K; Pohlman, J W; Reatherford, S R; Spargo, B J; Smith, D C

2005-02-01

Polycyclic aromatic hydrocarbons (PAHs) are common contaminants in terrestrial and aquatic environments and can represent a significant constituent of the carbon pool in coastal sediments. We report here the results of an 18-month seasonal study of PAH biodegradation and heterotrophic bacterial production and their controlling biogeochemical factors from 186 sediment samples taken in a tidally influenced freshwater estuary. For each sampling event, measurements were averaged from 25-45 stations covering approximately 250 km(2). There was a clear relationship between bacterial production and ambient temperature, but none between production and bottom water dissolved oxygen (DO) % saturation or PAH concentrations. In contrast with other studies, we found no effect of temperature on the biodegradation of naphthalene, phenanthrene, or fluoranthene. PAH mineralization correlated with bottom water DO saturation above 70% (r(2) > 0.99). These results suggest that the proportional utilization of PAH carbon to natural organic carbon is as much as three orders of magnitude higher during cooler months, when water temperatures are lower and DO % saturation is higher. Infusion of cooler, well-oxygenated water to the water column overlying contaminated sediments during the summer months may stimulate PAH metabolism preferentially over non-PAH organic matter.

Experimental determination of photostability and fluorescence-based detection of PAHs on the Martian surface

NASA Astrophysics Data System (ADS)

Dartnell, Lewis R.; Patel, Manish R.; Storrie-Lombardi, Michael C.; Ward, John M.; Muller, Jan-Peter

2012-05-01

Even in the absence of any biosphere on Mars, organic molecules, including polycyclic aromatic hydrocarbons (PAHs), are expected on its surface due to delivery by comets and meteorites of extraterrestrial organics synthesized by astrochemistry, or perhaps in situ synthesis in ancient prebiotic chemistry. Any organic compounds exposed to the unfiltered solar ultraviolet spectrum or oxidizing surface conditions would have been readily destroyed, but discoverable caches of Martian organics may remain shielded in the subsurface or within surface rocks. We have studied the stability of three representative polycyclic aromatic hydrocarbons (PAHs) in a Mars chamber, emulating the ultraviolet spectrum of unfiltered sunlight under temperature and pressure conditions of the Martian surface. Fluorescence spectroscopy is used as a sensitive indicator of remaining PAH concentration for laboratory quantification of molecular degradation rates once exposed on the Martian surface. Fluorescence-based instrumentation has also been proposed as an effective surveying method for prebiotic organics on the Martian surface. We find the representative PAHs, anthracene, pyrene, and perylene, to have persistence half-lives once exposed on the Martian surface of between 25 and 60 h of noontime summer UV irradiation, as measured by fluorescence at their peak excitation wavelength. This equates to between 4 and 9.6 sols when the diurnal cycle of UV light intensity on the Martian surface is taken into account, giving a substantial window of opportunity for detection of organic fluorescence before photodegradation. This study thus supports the use of fluorescence-based instrumentation for surveying recently exposed material (such as from cores or drill tailings) for native Martian organic molecules in rover missions.

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

NASA Astrophysics Data System (ADS)

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

2014-04-01

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

Variability in PAH-DNA adduct measurements in peripheral mononuclear cells: implications for quantitative cancer risk assessment.

PubMed

Dickey, C; Santella, R M; Hattis, D; Tang, D; Hsu, Y; Cooper, T; Young, T L; Perera, F P

1997-10-01

Biomarkers such as DNA adducts have significant potential to improve quantitative risk assessment by characterizing individual differences in metabolism of genotoxins and DNA repair and accounting for some of the factors that could affect interindividual variation in cancer risk. Inherent uncertainty in laboratory measurements and within-person variability of DNA adduct levels over time are putatively unrelated to cancer risk and should be subtracted from observed variation to better estimate interindividual variability of response to carcinogen exposure. A total of 41 volunteers, both smokers and nonsmokers, were asked to provide a peripheral blood sample every 3 weeks for several months in order to specifically assess intraindividual variability of polycyclic aromatic hydrocarbon (PAH)-DNA adduct levels. The intraindividual variance in PAH-DNA adduct levels, together with measurement uncertainty (laboratory variability and unaccounted for differences in exposure), constituted roughly 30% of the overall variance. An estimated 70% of the total variance was contributed by interindividual variability and is probably representative of the true biologic variability of response to carcinogenic exposure in lymphocytes. The estimated interindividual variability in DNA damage after subtracting intraindividual variability and measurement uncertainty was 24-fold. Inter-individual variance was higher (52-fold) in persons who constitutively lack the Glutathione S-Transferase M1 (GSTM1) gene which is important in the detoxification pathway of PAH. Risk assessment models that do not consider the variability of susceptibility to DNA damage following carcinogen exposure may underestimate risks to the general population, especially for those people who are most vulnerable.

Sediment PAHs and tumors in brown bullhead (Ameiurus nebulosus) at Featherstone National Wildlife Refuge, Virginia

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

Pinkney, A.E.; Sutherland, D.W.; Foley, R.E.

1995-12-31

Featherstone National Wildlife Refuge is located in Virginia along the Potomac River, about 35.4 kilometers southwest of Washington, DC. The study objective was to verify past observations of gross lesions in several fish species, previously collected from Potomac River tributaries for contaminant analysis. Thirty brown bullhead (Ameiurus nebulosus) were collected from Neabsco Creek, which borders the refuge, 29 were collected from Farm Creek, which bisects the refuge, and 30 were collected from Marumsco Creek, 1.75 km upstream. Sediment concentrations of polynuclear aromatic hydrocarbons (PAHS) were measured because elevated levels have been associated with skin and liver tumors in this species.more » The average concentration of total carcinogenic PAHs in sediments was: Farm Creek (0.34 ppm) < Marumsco Creek (0.63 ppm) < Neabsco Creek (1.37 ppm). The prevalence of skin neoplasms (squamous carcinomas and papillomas) was 3.4% in Farm Creek, 16.6% in Marumsco Creek, and 33.3% in Neabsco Creek. This ranking and the rankings of the total number of fish with tumors, invasive tumors, or non-parasitic lesions all followed the trend in sediment carcinogenic PAHs (p < 0.003; Jongheere-Terpstra test). The prevalence of liver carcinomas (O% at Farm Creek, 3.3% at Marumsco Creek, and 10% at Neabsco Creek) was of borderline significance (p = 0.06). The highest sediment concentrations of total (25.5 ppm) and carcinogenic (2.70 ppm) PAHs were found in Neabsco Creek near a complex of three marinas. Further sampling should be conducted in Neabsco Creek to determine the sources and extent of PAH contamination. Laboratory exposures are recommended for establishing a cause-effect linkage between sediment and tumor incidence. Additional sediment chemistry is needed to determine if other carcinogens are present.« less

Nitration of particle-associated PAHs and their derivatives (nitro-, oxy-, and hydroxy-PAHs) with NO 3 radicals

NASA Astrophysics Data System (ADS)

Zhang, Yang; Yang, Bo; Gan, Jie; Liu, Changgeng; Shu, Xi; Shu, Jinian

2011-05-01

The heterogeneous reactions of typical polycyclic aromatic hydrocarbons (PAHs) and their derivatives (nitro-, oxy-, and hydroxy-PAHs) adsorbed on azelaic acid particles with NO 3 radicals are investigated using a flow-tube reactor coupled to a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The mono-nitro-, di-nitro-, and poly-nitro-products from successive nitro-substitution reactions of PAHs and their derivatives are observed in real time with VUV-ATOFMS. 9-Nitroanthracene, anthraquinone, anthrone, 9,10-dinitroanthracene, 2-, 4-, and 9-nitrophenanthrene, 1-nitropyrene, 1,3-, 1,6-, and 1,8-dinitropyrene, 7-nitrobenzo[ a]anthracene, and benzo[ a]anthracene-7,12-dione are identified by GC/MS analysis of the reaction products of PAHs and their derivatives coated on the inner bottom surface of the conical flasks with NO 3 radicals. Other oxygenated products are tentatively assigned. 1-Nitropyrene is the only mono-nitrated product detected in the reaction of surface-bound pyrene with gas-phase NO 3 radicals. This phenomenon is different from what has been observed in previous studies of the gas-phase pyrene nitration, showing that 2-nitropyrene is the sole nitration product. The experimental results may reveal the discrepancies between the heterogeneous and homogeneous nitrations of pyrene.

Response of PAH-degrading genes to PAH bioavailability in the overlying water, suspended sediment, and deposited sediment of the Yangtze River.

PubMed

Xia, Xinghui; Xia, Na; Lai, Yunjia; Dong, Jianwei; Zhao, Pujun; Zhu, Baotong; Li, Zhihuang; Ye, Wan; Yuan, Yue; Huang, Junxiong

2015-06-01

The degrading genes of hydrophobic organic compounds (HOCs) serve as indicators of in situ HOC degradation potential, and the existing forms and bioavailability of HOCs might influence the distribution of HOC-degrading genes in natural waters. However, little research has been conducted to study the relationship between them. In the present study, nahAc and nidA genes, which act as biomarkers for naphthalene- and pyrene-degrading bacteria, were selected as model genotypes to investigate the response of polycyclic aromatic hydrocarbon (PAH)-degrading genes to PAH bioavailability in the overlying water, suspended sediment (SPS), and deposited sediment of the Yangtze River. The freely dissolved concentration, typically used to reflect HOC bioavailability, and total dissolved, as well as sorbed concentrations of PAHs were determined. Phylogenetic analysis showed that all the PAH-ring hydroxylating dioxygenase gene sequences of Gram-negative bacteria (PAH-RHD[GN]) were closely related to nahAc, nagAc, nidA, and uncultured PAH-RHD genes. The PAH-RHD[GN] gene diversity as well as nahAc and nidA gene copy numbers decreased in the following order: deposited sediment>SPS>overlying water. The nahAc and nidA gene abundance was not significantly correlated with environmental parameters but was significantly correlated with the bioavailable existing forms of naphthalene and pyrene in the three phases. The nahAc gene copy numbers in the overlying water and deposited sediment were positively correlated with freely dissolved naphthalene concentrations in the overlying and pore water phases, respectively, and so were nidA gene copy numbers. This study suggests that the distribution and abundance of HOC-degrading bacterial population depend on the HOC bioavailability in aquatic environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Annual variability of PAH concentrations in the Potomac River watershed

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

Maher, I.L.; Foster, G.D.

1995-12-31

Dynamics of organic contaminant transport in a large river system is influenced by annual variability in organic contaminant concentrations. Surface runoff and groundwater input control the flow of river waters. They are also the two major inputs of contaminants to river waters. The annual variability of contaminant concentrations in rivers may or may not represent similar trends to the flow changes of river waters. The purpose of the research is to define the annual variability in concentrations of polycyclic aromatic hydrocarbons (PAH) in riverine environment. To accomplish this, from March 1992 to March 1995 samples of Potomac River water weremore » collected monthly or bimonthly downstream of the Chesapeake Bay fall line (Chain Bridge) during base flow and main storm flow hydrologic conditions. Concentrations of selected PAHs were measured in the dissolved phase and the particulate phase via GC/MS. The study of the annual variability of PAH concentrations will be performed through comparisons of PAH concentrations seasonally, annually, and through study of PAH concentration river discharge dependency and rainfall dependency. For selected PAHs monthly and annual loadings will be estimated based on their measured concentrations and average daily river discharge. The monthly loadings of selected PAHs will be compared by seasons and annually.« less

Polycyclic aromatic hydrocarbons (PAHs) in atmospheric PM2.5 and PM10 at a coal-based industrial city: Implication for PAH control at industrial agglomeration regions, China

NASA Astrophysics Data System (ADS)

Wu, Di; Wang, Zongshuang; Chen, Jianhua; Kong, Shaofei; Fu, Xiao; Deng, Hongbing; Shao, Guofan; Wu, Gang

2014-11-01

Eighteen polycyclic aromatic hydrocarbons (PAHs) in PM2.5 and PM10 are identified and quantified at five sites of E'erduosi in 2005 by GC-MS. Total PAH concentrations in PM2.5 and PM10 are in the ranges of 0.58-145.01 ng m- 3 and 5.80-180.32 ng m- 3 for the five sites, decreasing as coal-chemical base site (ZGE) > heavy industrial site (QPJ) > residential site with heavy traffic (DS) > suburban site surrounded by grassland (HJQ) > background site (QGN) for both PM2.5 and PM10. PAH concentrations in the coal-chemical base site are 250 and 31.1 times of those in the background site. Flu, Pyr, Chr, BbF, BeP, IND and BghiP are abundant for the coal-chemical base site, totally accounting for 75% of the PAH concentrations. 4, 5 and 6 rings PAHs are dominant, accounting for 88.9-94.2% and 90.5-94.1% of PAHs in PM2.5 and PM10, respectively. Combustion-derived PAH concentrations cover 42%-84% and 75%-82% of PAHs in PM2.5 and PM10, indicating large amounts of combustion sources existed for them in E'erduosi. PAH compositions between PM2.5 and PM10 are quite different from each other for sites with few human activities (HJQ and QGN) by coefficient of divergence analysis. Results obtained from principal component analysis and diagnostic ratios indicate that coal combustion, vehicle emission, wood combustion and industrial processes are the main sources for PAHs in E'erduosi. According to BaP equivalent concentration, the potential health risk of PAHs in PM2.5 at the two industrial sites ZGE and QPJ are 537 and 460 times of those for the background site. And they are 4.3 and 3.7 times of those for the residential site. The potential PAH pollution in particles at other industrial agglomeration regions that occurred in China in recent years should be paid attention by the local government.

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

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

Toxicity and photoactivation of PAH mixtures in marine sediment

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

Swartz, R.; Ferraro, S.; Lamberson, J.

1995-12-31

The toxicity and toxicological photoactivation of mixtures of sediment-associated fluoranthene, phenanthrene, pyrene, and acenaphthene were determined using standard 10 d sediment toxicity tests with the marine amphipod, Rhepoxynius abronius. The four PAHs were spiked into sediment in a concentration series of either single compounds or an equitoxic mixture. Spiked sediment was stored at 4 C for 28 d before testing. Toxicity tests were conducted under fluorescent lighting. Survivors after 10 d in PAH-contaminated sediment were exposed for 1 h to UV light in the absence of sediment and then tested for their ability to bury in clean sediment. The 10more » d LC50s for single PAHs were 3.3, 2.2, 2.8, and 2.3 mg/g oc for fluoranthene, phenanthrene, pyrene, and acenaphthene, respectively. These LC50s were used to calculate the sum of toxic units ({Sigma}TU) of the four PAHs in the equitoxic mixture treatments. The {Sigma}TU LC50 was then calculated for the mixture treatments. If the toxicological interaction of the four PAHs in the mixture was additive, the {Sigma}TU LC50 should equal 1.0. The observed {Sigma}TU LC50 in the mixture was 1.55, indicating the interaction was slightly less than additive. UV enhancement of toxic effects of individual PAHs was correctly predicted by photophysical properties, i.e. pyrene and fluoranthene were photoactivated and phenanthrene and acenaphthene were not. UV effects in the mixture of four PAHs can be explained by the photoactivation of pyrene and fluoranthene alone.« less

Temporal variability in sediment PAHs accumulation in the northern Gulf of Mexico Shelf

NASA Astrophysics Data System (ADS)

Bam, W.; Maiti, K.; Adhikari, P. L.

2017-12-01

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous group of organic pollutants, some of which are known to be toxic, and/or carcinogenic to humans. The major source of these PAHs into the northern Gulf of Mexico (NGOM) are Mississippi River discharge, coastal erosion, atmospheric deposition, and numerous natural oil seeps and spills. In addition to these background source of PAHs, the Deepwater Horizon (DWH) oil spill in 2010 added 21,000 tons of PAHs into the NGOM water. In this study, we measured PAHs distribution and accumulation rates in coastal sediments near the Mississippi River mouth in 2011 and 2015 to understand the effect of DWH oil spill in PAHs accumulation in coastal sediments. Sediment cores were collected and sliced at 1 cm interval to measure PAHs concentration, and to estimate 210Pb-based sedimentation and the PAHs' accumulation rates. The results showed that the sediment deposition rates in this region varied between 0.5 to 0.9 cm/yr. The results also showed that the concentration of total PAHs (ΣPAH43) and their accumulation rates vary between 68 - 100 ng g-1 and 7 - 160 ng cm-2 yr-1, respectively. While the PAHs accumulation rate in coastal sediment varied over the years, there is no significant variation in PAHs accumulation rate before and after the DWH oil spill.

Co-formation and co-release of genotoxic PAHs, alkyl-PAHs and soot nanoparticles from gasoline direct injection vehicles

NASA Astrophysics Data System (ADS)

Muñoz, Maria; Haag, Regula; Honegger, Peter; Zeyer, Kerstin; Mohn, Joachim; Comte, Pierre; Czerwinski, Jan; Heeb, Norbert V.

2018-04-01

Gasoline direct injection (GDI) vehicles quickly replace traditional port-fuel injection (PFI) vehicles in Europe reaching about 50 million vehicles on roads in 2020. GDI vehicles release large numbers of soot nanoparticles similar to conventional diesel vehicles without particle filters. These exhausts will increasingly affect air quality in European cities. We hypothesized that such particles are released together with polycyclic aromatic hydrocarbons (PAHs) formed under the same combustion conditions. Emission data of a fleet of 7 GDI vehicles (1.2-1.8 L) including Euro-3,-4,-5 and -6 technologies revealed substantial particle emissions on average of 2.5 × 1012 particles km-1 in the cold worldwide harmonized light vehicle test cycle (cWLTC), the future European legislative driving cycle. Particle emissions increased 2-3 orders of magnitude during acceleration like CO, indicating that transient driving produces fuel-rich conditions with intense particle formation. For comparison, an Euro-5 diesel vehicle (1.6 L) equipped with a particle filter released 3.9 × 1010 particles km-1 (cWLTC), clearly within the Euro-5/6 limit value of 6.0 × 1011 particles km-1 and 64-fold below the GDI fleet average. PAH and alkyl-PAH emissions of the GDI vehicles also exceeded those of the diesel vehicle. Mean GDI emissions of 2-, 3-, 4-, 5- and 6-ring PAHs in the cWLTC were 240, 44, 5.8, 0.5 and 0.4 μg km-1, those of the diesel vehicle were only 8.8, 7.1, 8.6, 0.02 and 0.02 μg km-1, respectively. Thus mean PAH emissions of the GDI fleet were 2 orders of magnitude higher than the bench mark diesel vehicle. A comparison of the toxicity equivalent concentrations (TEQ) in the cWLTC of the GDI fleet and the diesel vehicle revealed that GDI vehicles released 200-1700 ng TEQ m-3 genotoxic PAHs, being 6-40 times higher than the diesel vehicle with 45 ng TEQ km-1. The co-release of genotoxic PAHs adsorbed on numerous soot nanoparticles is critical due to the Trojan horse effect

Review of PAH contamination in food products and their health hazards.

PubMed

Bansal, Vasudha; Kim, Ki-Hyun

2015-11-01

Public concern over the deleterious effects of polycyclic aromatic hydrocarbons (PAHs) has grown rapidly due to recognition of their toxicity, carcinogenicity, and teratogenicity. The aim of this review is to describe the status of PAH pollution among different food types, the route of dietary intake, measures for its reduction, and legislative approaches to control PAH. To this end, a comprehensive review is outlined to evaluate the status of PAH contamination in many important food categories along with dietary recommendations. Our discussion is also extended to describe preventive measures to reduce PAH in food products to help reduce the risks associated with human intake. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

A Systematic Review of Paradoxical Adipose Hyperplasia (PAH) Post-Cryolipolysis.

PubMed

Ho, Derek; Jagdeo, Jared

2017-01-01

Body sculpting, or body contouring, is among the fastest growing areas in cosmetic dermatology. Cryolipolysis, or "fat freezing," was FDA-cleared (CoolSculpting System, ZELTIQ Aesthetics, Pleasanton, CA) initially in 2010 for fat removal of the anks, and subsequently received FDA-clearance for other anatomical locations. Over the past several years, there have been increasing published reports and physician discussion regarding paradoxical adipose hyperplasia (PAH) post-cryolipolysis, previously identified as a "rare" adverse effect. To review published reports of PAH post-cryolipolysis, expand on previously proposed hypothesis of PAH, and provide rec- ommendations for prevention and treatment of PAH. On July 26, 2016, we systematically searched the computerized medical bibliographic databases PubMed, EMBASE, Web of Science, and CINAHL with the search term "cryolipolysis." A total of 314 records were returned from our search terms and 10 records were found to be suitable for our review. We identi- ed a total of 16 cases of PAH post-cryolipolysis in the published literature. Based upon the published literature, we identi ed that the current incidence of PAH may be higher than previously re- ported. Although the pathoetiology of PAH is currently unknown, we hypothesize that some adipocytes may be "naturally selected" for survival due to their inherent tolerance to cryolipolysis. We believe that while cryolipolysis is an effective non-invasive treatment option for body contouring, physicians and patients should be aware of PAH as a potential adverse effect and treatment options. J Drugs Dermatol. 2017;16(1):62-67..

Optimizing contaminant desorption and bioavailability in dense slurry systems. 2. PAH bioavailability and rates of degradation.

PubMed

Kim, Han S; Weber, Walter J

2005-04-01

The effects of mechanical mixing on rates of polycyclic aromatic hydrocarbon (PAH) biodegradation in dense geosorbent slurry (67% solids content, w/w) systems were evaluated using laboratory-scale intermittently mixed batch bioreactors. A PAH-contaminated soil and a phenanthrene-sorbed mineral sorbent (alpha-Al2O3) were respectively employed as slurry solids in aerobic and anaerobic biodegradation studies. Both slurries exhibited a characteristic behavior of pseudoplastic non-Newtonian fluids, and the impeller revolution rate and its diameter had dramatic impacts on power and torque requirements in their laminar flow mixing. Rates of phenanthrene biodegradation were markedly enhanced by relatively low-level auger mixing under both aerobic and anaerobic (denitrifying) conditions. Parameters for empirical models correlating biodegradation rate coefficient (k(b)) values to the degree of mixing were similar to those for correlations between mass transfer (desorption) rate coefficient (k(r)) values for rapidly desorbing fractions of soil organic matter and degree of mixing reported in a companion study, supporting a conclusion that performance-efficient and cost-effective enhancements of PAH mass transfer (desorption) and its biodegradation processes can be achieved by the introduction of optimal levels of reactor-scale mechanical mixing.

On the driving force of PAH production

NASA Technical Reports Server (NTRS)

Frenklach, Michael

1989-01-01

The kinetic factors affecting the production of polycyclic aromatic hydrocarbons (PAH) in high-temperature pyrolysis and combustion environments are analyzed. A lumped kinetic model representing polymerization-type growth by one irreversible step and two reversible steps is considered. It is shown that at high temperatures, PAH growth is controlled by the superequilibrium of hydrogen atoms; at low temperatures and low H2 concentrations, the PAH growth rate is proportional to the rate of the H-abstraction of a hydrogen atom from aromatic molecules; while at low temperatures and high H2 concentrations, it is controlled by the thermodynamics of the H-abstraction and the kinetics of acetylene addition to aromatic radicals. The presence of oxygen mainly affects the small-molecule reactions during the induction period.

PAH (Polycyclic Aromatic Hydrocarbon) bioaccumulation and PAHs/shell weight index in Ruditapes philippinarum (Adams & Reeve, 1850) from the Vallona lagoon (northern Adriatic Sea, NE Italy).

PubMed

Cacciatore, Federica; Bernarello, Valentina; Boscolo Brusà, Rossella; Sesta, Giulio; Franceschini, Gianluca; Maggi, Chiara; Gabellini, Massimo; Lamberti, Clauda Virno

2018-02-01

The Vallona lagoon is a transitional area located in the Po River delta (NE, ITALY) traditionally exploited for Manila clam (Ruditapes philippinarum) farming. During 2007-2008, a pipeline was buried in the middle of the lagoon to connect an off-shore structure to facilities on land. PAH levels were monitored in Manila clams and sediments before, during and after the pipeline construction to assess the impact of the activities through the pattern of distribution of the PAH compounds. PAH bioaccumulation in clams displayed seasonal fluctuations with higher levels in autumnal and wintry surveys than in spring-summer. Principal component analysis applied to PAHs in clams highlighted a petrogenic input during ante operam period and a pyrolytic origin during the burying activities. On the contrary, sediment PAH concentrations resulted quite similar both among sites and periods. Biota-Sediment-Accumulation-Factor values also confirmed that sediments were not the major source of PAH pollution for clams in this study. The welfare of clams was examined through two physiological indices (condition index and survival in air) to check the effects of the activities on a commercial resource. Both physiological indices exhibited seasonal variations connected to natural endogenous and exogenous factors; however survival in air was the most sensitive index in highlighting the effects of the pipeline burying activities. Finally, to ensure that PAH bioavailability assessment was not affected by seasonal variation of soft tissues of molluscs, PAHs/shell weight index was applied. Higher levels of this index were observed before and during the burying activities, whilst, after that, values significantly lowered. Moreover, the normalization enabled us to highlight the PAH uptake from clams in some particular periods and to compare different populations in a long-term biomonitoring program with data obtained from different periods of the year. Copyright © 2017 Elsevier Inc. All rights

Effect of a cationic surfactant on the volatilization of PAHs from soil.

PubMed

Lu, Li; Zhu, Lizhong

2012-06-01

Cationic surfactants are common in soils because of their use in daily cosmetic and cleaning products, and their use as a soil amendment for the mitigation and remediation of organic contaminated soils has been proposed. Such surfactant may affect the transfer and fate of organic contaminants in the environment. This study investigated the effect of a cationic surfactant, dodecylpyridinium bromide (DDPB), on the volatilization of polycyclic aromatic hydrocarbons (PAHs) from a paddy soil. The volatilization of PAHs from moist soil amended with different concentrations of DDPB was tested in an open system. The specific effects of DDPB on the liquid-vapor and solid-vapor equilibriums of PAHs were separately investigated in closed systems by headspace analysis. DDPB affects both liquid-vapor and solid-vapor processes of PAHs in soil. At DDPB concentrations below the critical micelle concentration (CMC), movement of PAHs from the bulk solution to the gas-liquid interface appeared to be facilitated by interaction between PAHs and the surfactant monomers adsorbed at the gas-liquid interface, promoting the volatilization of PAHs from solution. However, when DDPB was greater than the CMC, volatilization was inhibited due to the solubilization of PAHs by micelles. On the other hand, the formation of sorbed surfactant significantly inhibited the solid-vapor volatilization of PAHs. The overall effect of the two simultaneous effects of DDPB on liquid-vapor and solid-vapor processes was a decreased volatilization loss of PAHs from soil. Inhibition of PAH volatilization was more significant for the soil with a lower moisture content.

Polycyclic aromatic hydrocarbon (PAH) emissions from a coal-fired pilot FBC system.

PubMed

Liu, K; Han, W; Pan, W P; Riley, J T

2001-06-29

Due to the extensive amount of data suggesting the hazards of these compounds, 16 polycyclic aromatic hydrocarbons (PAHs) are on the Environmental Protection Agency (EPA) Priority Pollutant List. Emissions of these PAHs in the flue gas from the combustion of four coals were measured during four 1000h combustion runs using the 0.1MW heat-input (MWth) bench-scale fluidized bed combustor (FBC). An on-line sampling system was designed for the 16 PAHs, which consisted of a glass wool filter, condenser, glass fiber filter, Teflon filter, and a Tenax trap. The filters and Tenax were extracted by methylene chloride and hexane, respectively, followed by GC/MS analysis using the selective ion monitoring (SIM) mode. In this project, the effects of operating parameters, limestone addition, chlorine content in the coal, and Ca/S molar ratio on the emissions of PAHs were studied. The results indicated that the emissions of PAHs in an FBC system are primarily dependent on the combustion temperature and excess air ratio. The injection of secondary air with high velocity in the freeboard effectively reduces PAH emissions. The addition of extra limestone can promote the formation of PAHs in the FBC system. Chlorine in the coal can possibly lead to large benzene ring PAH formation during combustion. The total PAH emission increases with an increase in the sulfur content of coal. Incomplete combustion results in PAHs with four or more benzene rings. High efficiency combustion results in PAHs with two or three benzene rings.

Yeast Pah1p Phosphatidate Phosphatase Is Regulated by Proteasome-mediated Degradation*

PubMed Central

Pascual, Florencia; Hsieh, Lu-Sheng; Soto-Cardalda, Aníbal; Carman, George M.

2014-01-01

Yeast PAH1-encoded phosphatidate phosphatase is the enzyme responsible for the production of the diacylglycerol used for the synthesis of triacylglycerol that accumulates in the stationary phase of growth. Paradoxically, the growth phase-mediated inductions of PAH1 and phosphatidate phosphatase activity do not correlate with the amount of Pah1p; enzyme abundance declined in a growth phase-dependent manner. Pah1p from exponential phase cells was a relatively stable protein, and its abundance was not affected by incubation with an extract from stationary phase cells. Recombinant Pah1p was degraded upon incubation with the 100,000 × g pellet fraction of stationary phase cells, although the enzyme was stable when incubated with the same fraction of exponential phase cells. MG132, an inhibitor of proteasome function, prevented degradation of the recombinant enzyme. Endogenously expressed and plasmid-mediated overexpressed levels of Pah1p were more abundant in the stationary phase of cells treated with MG132. Pah1p was stabilized in mutants with impaired proteasome (rpn4Δ, blm10Δ, ump1Δ, and pre1 pre2) and ubiquitination (hrd1Δ, ubc4Δ, ubc7Δ, ubc8Δ, and doa4Δ) functions. The pre1 pre2 mutations that eliminate nearly all chymotrypsin-like activity of the 20 S proteasome had the greatest stabilizing effect on enzyme levels. Taken together, these results supported the conclusion that Pah1p is subject to proteasome-mediated degradation in the stationary phase. That Pah1p abundance was stabilized in pah1Δ mutant cells expressing catalytically inactive forms of Pah1p and dgk1Δ mutant cells with induced expression of DGK1-encoded diacylglycerol kinase indicated that alteration in phosphatidate and/or diacylglycerol levels might be the signal that triggers Pah1p degradation. PMID:24563465

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

Generation and distribution of PAHs in the process of medical waste incineration

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

Chen, Ying, E-mail: echochen327@163.com; National Center of Solid Waste Management, Ministry of Environmental Protection, Beijing 100029; Zhao, Rongzhi

Highlights: ► PAHs generation and distribution features of medical waste incineration are studied. ► More PAHs were found in fly ash than that in bottom ash. ► The highest proportion of PAHs consisted of the seven most carcinogenic ones. ► Increase of free oxygen molecule and burning temperature promote PAHs degradation. ► There is a moderate positive correlation between total PCDD/Fs and total PAHs. - Abstract: After the deadly earthquake on May 12, 2008 in Wenchuan county of China, several different incineration approaches were used for medical waste disposal. This paper investigates the generation properties of polycyclic aromatic hydrocarbons (PAHs)more » during the incineration. Samples were collected from the bottom ash in an open burning slash site, surface soil at the open burning site, bottom ash from a simple incinerator, bottom ash generated from the municipal solid waste (MSW) incinerator used for medical waste disposal, and bottom ash and fly ash from an incinerator exclusively used for medical waste. The species of PAHs were analyzed, and the toxicity equivalency quantities (TEQs) of samples calculated. Analysis results indicate that the content of total PAHs in fly ash was 1.8 × 10{sup 3} times higher than that in bottom ash, and that the strongly carcinogenic PAHs with four or more rings accumulated sensitively in fly ash. The test results of samples gathered from open burning site demonstrate that Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT) and other PAHs were inclined to migrate into surrounding environment along air and surface watershed corridors, while 4- to 6-ring PAHs accumulated more likely in soil. Being consistent with other studies, it has also been confirmed that increases in both free oxygen molecules and combustion temperatures could promote the decomposition of polycyclic PAHs. In addition, without the influence of combustion conditions, there is a positive correlation

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.

Characteristics and survival of adult Swedish PAH and CTEPH patients 2000-2014.

PubMed

Rådegran, Göran; Kjellström, Barbro; Ekmehag, Björn; Larsen, Flemming; Rundqvist, Bengt; Blomquist, Sofia Berg; Gustafsson, Carola; Hesselstrand, Roger; Karlsson, Monica; Kornhall, Björn; Nisell, Magnus; Persson, Liselotte; Ryftenius, Henrik; Selin, Maria; Ullman, Bengt; Wall, Kent; Wikström, Gerhard; Willehadson, Maria; Jansson, Kjell

2016-08-01

The Swedish Pulmonary Arterial Hypertension Register (SPAHR) is an open continuous register, including pulmonary arterial hypertension (PAH) and chronic thromboembolic pulmonary hypertension (CTEPH) patients from 2000 and onwards. We hereby launch the first data from SPAHR, defining baseline characteristics and survival of Swedish PAH and CTEPH patients. Incident PAH and CTEPH patients 2008-2014 from all seven Swedish PAH-centres were specifically reviewed. There were 457 PAH (median age: 67 years, 64% female) and 183 CTEPH (median age: 70 years, 50% female) patients, whereof 77 and 81%, respectively, were in functional class III-IV at diagnosis. Systemic hypertension, diabetes, ischaemic heart disease and atrial fibrillation were common comorbidities, particularly in those >65 years. One-, 3- and 5-year survival was 85%, 71% and 59% for PAH patients. Corresponding numbers for CTEPH patients with versus without pulmonary endarterectomy were 96%, 89% and 86% versus 91%, 75% and 69%, respectively. In 2014, the incidence of IPAH/HPAH, associated PAH and CTEPH was 5, 3 and 2 per million inhabitants and year, and the prevalence was 25, 24 and 19 per million inhabitants. The majority of the PAH and CTEPH patients were diagnosed at age >65 years, in functional class III-IV, and exhibiting several comorbidities. PAH survival in SPAHR was similar to other registers.

Enhanced PM10 bounded PAHs from shipping emissions

NASA Astrophysics Data System (ADS)

Pongpiachan, S.; Hattayanone, M.; Choochuay, C.; Mekmok, R.; Wuttijak, N.; Ketratanakul, A.

2015-05-01

Earlier studies have highlighted the importance of maritime transport as a main contributor of air pollutants in port area. The authors intended to investigate the effects of shipping emissions on the enhancement of PM10 bounded polycyclic aromatic hydrocarbons (PAHs) and mutagenic substances in an industrial area of Rayong province, Thailand. Daily PM10 speciation data across two air quality observatory sites in Thailand during 2010-2013 were collected. Diagnostic binary ratios of PAH congeners, analysis of variances (ANOVA), and principal component analysis (PCA) were employed to evaluate the enhanced genotoxicity of PM10 during the docking period. Significant increase of PAHs and mutagenic index (MI) of PM10 were observed during the docking period in both sampling sites. Although stationary sources like coal combustions from power plants and vehicular exhausts from motorway can play a great role in enhancing PAH concentrations, regulating shipping emissions from diesel engine in the port area like Rayong is predominantly crucial.

Degradation of PAHs in soil by Lasiodiplodia theobromae and enhanced benzo[a]pyrene degradation by the addition of Tween-80.

PubMed

Wang, Cuiping; Liu, Haibin; Li, Jing; Sun, Hongwen

2014-09-01

Benzo[a]pyrene (BaP), a five-ring polycyclic aromatic hydrocarbon (PAH), which has carcinogenic potency, is highly recalcitrant and resistant to microbial degradation. A novel fungus, Lasiodiplodia theobromae (L. theobromae), which can degrade BaP as a sole carbon source in liquid, was isolated in our laboratory. To prompt the further application of L. theobromae in remediation of sites polluted by BaP and other PAHs, the present study was targeted toward the removal of BaP and PAHs from soil by L. theobromae. The degradation of BaP by L. theobromae was studied using a soil spiked with 50 mg/kg BaP. L. theobromae could remove 32.1 % of the BaP after 35 days of cultivation. Phenanthrene (PHE) inhibited BaP degradation as a competitive substrate. The tested surfactants enhanced BaP degradation in soil by different extents, and a removal rate of 92.1 % was achieved at a Tween-80 (TW-80) concentration of 5 g/kg. It was revealed that TW-80 could not only enhance BaP bioavailability by increasing its aqueous solubility and decreasing the size of its colloid particles but also increase enzyme secretion from L. theobromae and the population of L. theobromae. Moreover, ergosterol content together with the biomass C indicated the increase in L. theobromae biomass during the BaP biodegradation process in soils. Finally, a soil from a historically PAH-contaminated field at Beijing Coking Plant in China was tested to assess the feasibility of applying L. theobromae in the remediation of polluted sites. The total removal rate of PAHs by L. theobromae was 53.3 %, which is 13.1 % higher than that by Phanerochaete chrysosporium (P. chrysosporium), an effective PAH degrader. The addition of TW-80 to the field soil further enhanced PAH degradation to 73.2 %. Hence, L. theobromae is a promising novel strain to be implemented in the remediation of soil polluted by PAHs.

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.

Behaviour of polycyclic aromatic hydrocarbons (PAH) in soils under freeze-thaw cycles

NASA Astrophysics Data System (ADS)

Zschocke, Anne; Schönborn, Maike; Eschenbach, Annette

2010-05-01

The arctic region will be one of the most affected regions by climate change due to the predicted temperature rise. As a result of anthropogenic actions as mining, exploration and refining as well as atmospheric transport pollutions can be found in arctic soils. Therefore questions on the behaviour of organic contaminants in permafrost influenced soils are of high relevance. First investigations showed that permafrost can act as a semi-permeable layer for PAH (Curtosi et al., 2007). Therefore it can be assumed that global warming could result in a mobilization of PAH in these permafrost influenced soils. On the other hand a low but detectable mineralization of organic hydrocarbons by microorganisms under repeated freeze-thaw cycles was analysed (Börresen et al. 2007, Eschenbach et al. 2000). In this study the behaviour and distribution of PAH under freezing and periodically freezing and thawing were investigated in laboratory column experiments with spiked soil materials. Two soil materials which are typical for artic regions, a organic matter containing melt water sand and a well decomposed peat, were homogeneously spiked with a composite of a crude oil and the PAH anthracene and benzo(a)pyrene. After 14days preincubation time the soil material was filled in the laboratory columns (40cm high and 10 cm in diameter). Based on studies by Chuvilin et al. (2001) the impact of freezing of the upper third of the column from the surface downwards was examined. The impact of freezing was tested in two different approaches the first one with a single freezing step and the second one with a fourfold repeated cycle of freezing and thawing which takes about 6 or 7 days each. The experimental design and very first results will be shown and discussed. In some experiments with the peat a higher concentration of anthracene and benzo(a)pyrene could be detected below the freezing front in the unfrozen part of the column. Whereas the concentration of PAH had slightly decreased in

Biodegradation of PAHs and PCBs in soils and sludges

USGS Publications Warehouse

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

2007-01-01

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

Spatial Distribution of Polycyclic Aromatic Hydrocarbon (PAH) Concentrations in Soils from Bursa, Turkey.

PubMed

Karaca, Gizem

2016-02-01

The objectives of this study were to identify regional variations in soil polycyclic aromatic hydrocarbon (PAH) contamination in Bursa, Turkey, and to determine the distributions and sources of various PAH species and their possible sources. Surface soil samples were collected from 20 different locations. The PAH concentrations in soil samples were analyzed using gas chromatography-mass spectrometry (GC-MS). The total PAH concentrations (∑12 PAH) varied spatially between 8 and 4970 ng/g dry matter (DM). The highest concentrations were measured in soils taken from traffic+barbecue+ residential areas (4970 ng/g DM) and areas with cement (4382 ng/g DM) and iron-steel (4000 ng/g DM) factories. In addition, the amounts of ∑7 carcinogenic PAH ranged from 1 to 3684 ng/g DM, and between 5 and 74 % of the total PAHs consisted of such compounds. Overall, 4-ring PAH compounds (Fl, Pyr, BaA and Chr) were dominant in the soil samples, with 29-82 % of the ∑12 PAH consisting of 4-ring PAH compounds. The ∑12 BaPeq values ranged from 0.1 to 381.8 ng/g DM. Following an evaluation of the molecular diagnostic ratios, it was concluded that the PAH pollution in Bursa soil was related to pyrolytic sources; however, the impact of petrogenic sources should not be ignored.

Mechanism-based classification of PAH mixtures to predict carcinogenic potential

DOE PAGES

Tilton, Susan C.; Siddens, Lisbeth K.; Krueger, Sharon K.; ...

2015-04-22

We have previously shown that relative potency factors and DNA adduct measurements are inadequate for predicting carcinogenicity of certain polycyclic aromatic hydrocarbons (PAHs) and PAH mixtures, particularly those that function through alternate pathways or exhibit greater promotional activity compared to benzo[ a]pyrene (BaP). Therefore, we developed a pathway based approach for classification of tumor outcome after dermal exposure to PAH/mixtures. FVB/N mice were exposed to dibenzo[ def,p]chrysene (DBC), BaP or environmental PAH mixtures (Mix 1-3) following a two-stage initiation/promotion skin tumor protocol. Resulting tumor incidence could be categorized by carcinogenic potency as DBC>>BaP=Mix2=Mix3>Mix1=Control, based on statistical significance. Gene expression profilesmore » measured in skin of mice collected 12 h post-initiation were compared to tumor outcome for identification of short-term bioactivity profiles. A Bayesian integration model was utilized to identify biological pathways predictive of PAH carcinogenic potential during initiation. Integration of probability matrices from four enriched pathways (p<0.05) for DNA damage, apoptosis, response to chemical stimulus and interferon gamma signaling resulted in the highest classification accuracy with leave-one-out cross validation. This pathway-driven approach was successfully utilized to distinguish early regulatory events during initiation prognostic for tumor outcome and provides proof-of-concept for using short-term initiation studies to classify carcinogenic potential of environmental PAH mixtures. As a result, these data further provide a ‘source-to outcome’ model that could be used to predict PAH interactions during tumorigenesis and provide an example of how mode-of-action based risk assessment could be employed for environmental PAH mixtures.« less

Incidence of real-world automotive parent and halogenated PAH in urban atmosphere.

PubMed

Gao, Pan-Pan; Zhao, Yi-Bo; Ni, Hong-Gang

2018-06-01

This study reports results from a tunnel experiment impact of real-world traffic-related particle and gas parent and halogenated polycyclic aromatic hydrocarbons (PAHs and HPAHs) on urban air. The traffic related emission characteristics and subsequent environmental behavior of these compounds were investigated. To understand the significance of real-world transport emissions to the urban air, traffic-related mass emissions of PAHs and HPAHs were estimated based on measured emission factors. According to our results, PAHs and HPAHs emissions via particulate phase were greater than those via gaseous phase; particles in 2.1-3.3 μm size fraction, have the major contribution to particulate PAHs and HPAHs emissions. Over all, contribution of traffic-related emission of PAHs (only ∼3% of the total PAHs emission in China) is an overstated source of PAHs pollution in China. Actually, exhaust pipe emission contributed much less than the total traffic-related emission of pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of Warfarin Treatment on Survival of Patients With Pulmonary Arterial Hypertension (PAH) in the Registry to Evaluate Early and Long-Term PAH Disease Management (REVEAL)

PubMed Central

Preston, Ioana R.; Roberts, Kari E.; Miller, Dave P.; Sen, Ginny P.; Selej, Mona; Benton, Wade W.; Hill, Nicholas S.

2015-01-01

Background— Long-term anticoagulation is recommended in idiopathic pulmonary arterial hypertension (IPAH). In contrast, limited data support anticoagulation in pulmonary arterial hypertension (PAH) associated with systemic sclerosis (SSc-PAH). We assessed the effect of warfarin anticoagulation on survival in IPAH and SSc-PAH patients enrolled in Registry to Evaluate Early and Long-term PAH Disease Management (REVEAL), a longitudinal registry of group I PAH. Methods and Results— Patients who initiated warfarin on study (n=187) were matched 1:1 with patients never on warfarin, by enrollment site, etiology, and diagnosis status. Descriptive analyses were conducted to compare warfarin users and nonusers by etiology. Survival analyses with and without risk adjustment were performed from the time of warfarin initiation or a corresponding quarterly update in matched pairs to avoid immortal time bias. Time-varying covariate models were used as sensitivity analyses. Mean warfarin treatment was 1 year; mean international normalized ratios were 1.9 (IPAH) and 2.0 (SSc-PAH). Two-thirds of patients initiating warfarin discontinued treatment before the last study assessment. There was no survival difference with warfarin in IPAH patients (adjusted hazard ratio, 1.37; P=0.21) or in SSc-PAH patients (adjusted hazard ratio, 1.60; P=0.15) in comparison with matched controls. However, SSc-PAH patients receiving warfarin within the previous year (hazard ratio, 1.57; P=0.031) or any time postbaseline (hazard ratio, 1.49; P=0.046) had increased mortality in comparison with warfarin-naïve patients. Conclusions— No significant survival advantage was observed in IPAH patients who started warfarin. In SSc-PAH patients, long-term warfarin was associated with poorer survival than in patients not receiving warfarin, even after adjusting for confounders. Clinical Trial Registration— URL: http://www.clinicaltrials.gov. Unique identifier: NCT00370214. PMID:26510696

Effect of Warfarin Treatment on Survival of Patients With Pulmonary Arterial Hypertension (PAH) in the Registry to Evaluate Early and Long-Term PAH Disease Management (REVEAL).

PubMed

Preston, Ioana R; Roberts, Kari E; Miller, Dave P; Sen, Ginny P; Selej, Mona; Benton, Wade W; Hill, Nicholas S; Farber, Harrison W

2015-12-22

Long-term anticoagulation is recommended in idiopathic pulmonary arterial hypertension (IPAH). In contrast, limited data support anticoagulation in pulmonary arterial hypertension (PAH) associated with systemic sclerosis (SSc-PAH). We assessed the effect of warfarin anticoagulation on survival in IPAH and SSc-PAH patients enrolled in Registry to Evaluate Early and Long-term PAH Disease Management (REVEAL), a longitudinal registry of group I PAH. Patients who initiated warfarin on study (n=187) were matched 1:1 with patients never on warfarin, by enrollment site, etiology, and diagnosis status. Descriptive analyses were conducted to compare warfarin users and nonusers by etiology. Survival analyses with and without risk adjustment were performed from the time of warfarin initiation or a corresponding quarterly update in matched pairs to avoid immortal time bias. Time-varying covariate models were used as sensitivity analyses. Mean warfarin treatment was 1 year; mean international normalized ratios were 1.9 (IPAH) and 2.0 (SSc-PAH). Two-thirds of patients initiating warfarin discontinued treatment before the last study assessment. There was no survival difference with warfarin in IPAH patients (adjusted hazard ratio, 1.37; P=0.21) or in SSc-PAH patients (adjusted hazard ratio, 1.60; P=0.15) in comparison with matched controls. However, SSc-PAH patients receiving warfarin within the previous year (hazard ratio, 1.57; P=0.031) or any time postbaseline (hazard ratio, 1.49; P=0.046) had increased mortality in comparison with warfarin-naïve patients. No significant survival advantage was observed in IPAH patients who started warfarin. In SSc-PAH patients, long-term warfarin was associated with poorer survival than in patients not receiving warfarin, even after adjusting for confounders. URL: http://www.clinicaltrials.gov. Unique identifier: NCT00370214. © 2015 The Authors.

Accelerated degradation of PAHs using edaphic biostimulants obtained from sewage sludge and chicken feathers.

PubMed

Rodríguez-Morgado, Bruno; Gómez, Isidoro; Parrado, Juan; García, Carlos; Hernández, Teresa; Tejada, Manuel

2015-12-30

We studied in the laboratory the bioremediation effects over a 100-day period of three edaphic biostimulants (BS) obtained from sewage sludge (SS) and from two different types of chicken feathers (CF1 and CF2), in a soil polluted with three polycyclic aromatic hydrocarbons (PAH) (phenanthrene, Phe; pyrene, Py; and benzo(a)pyrene, BaP), at a concentration of 100 mg kg(-1) soil. We determined their effects on enzymatic activities and on soil microbial community. Those BS with larger amounts of proteins and a higher proportion of peptides (<300 daltons), exerted a greater stimulation on the soil biochemical properties and microbial community, possibly because low molecular weight proteins can be easily assimilated by soil microorganisms. The soil dehydrogenase, urease, β-glucosidase and phosphatase activities and microbial community decreased in PAH-polluted soil. This decrease was more pronounced in soils contaminated with BaP than with Py and Phe. The application of the BS to PAH-polluted soils decreased the inhibition of the soil biological properties, principally at 7 days into the experiment. This decrease was more pronounced in soils contaminated with BaP than with Py and Phe and was higher in polluted soils amended with CF2, followed by SS and CF1, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Characteristics of PAHs in farmland soil and rainfall runoff in Tianjin, China.

PubMed

Shi, Rongguang; Xu, Mengmeng; Liu, Aifeng; Tian, Yong; Zhao, Zongshan

2017-10-14

Rainfall runoff can remove certain amounts of pollutants from contaminated farmland soil and result in a decline in water quality. However, the leaching behaviors of polycyclic aromatic hydrocarbons (PAHs) with rainfall have been rarely reported due to wide variations in the soil compositions, rainfall conditions, and sources of soil PAHs in complex farmland ecosystems. In this paper, the levels, spatial distributions, and composition profiles of PAHs in 30 farmland soil samples and 49 rainfall-runoff samples from the Tianjin region in 2012 were studied to investigate their leaching behaviors caused by rainfall runoff. The contents of the Σ 16 PAHs ranged from 58.53 to 3137.90 μg/kg in the soil and 146.58 to 3636.59 μg/L in the runoff. In total, most of the soil sampling sites (23 of 30) were contaminated, and biomass and petroleum combustion were proposed as the main sources of the soil PAHs. Both the spatial distributions of the soil and the runoff PAHs show a decreasing trend moving away from the downtown, which suggested that the leaching behaviors of PAHs in a larger region during rainfall may be mainly affected by the compounds themselves. In addition, 4- and 5-ring PAHs are the dominant components in farmland soil and 3- and 4-ring PAHs dominate the runoff. Comparisons of the PAH pairs and enrichment ratios showed that acenaphthylene, acenaphthene, benzo[a]anthracene, chrysene, and fluoranthene were more easily transferred into water systems from soil than benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, and indeno[123-cd]pyrene, which indicated that PAHs with low molecular weight are preferentially dissolved due to their higher solubility compared to those with high molecular weight.

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.

Coal-tar-based sealcoated pavement: a major PAH source to urban stream sediments.

PubMed

Witter, Amy E; Nguyen, Minh H; Baidar, Sunil; Sak, Peter B

2014-02-01

We used land-use analysis, PAH concentrations and assemblages, and multivariate statistics to identify sediment PAH sources in a small (~1303 km(2)) urbanizing watershed located in South-Central, Pennsylvania, USA. A geographic information system (GIS) was employed to quantify land-use features that may serve as PAH sources. Urban PAH concentrations were three times higher than rural levels, and were significantly and highly correlated with combined residential/commercial/industrial land use. Principal components analysis (PCA) was used to group sediments with similar PAH assemblages, and correlation analysis compared PAH sediment assemblages to common PAH sources. The strongest correlations were observed between rural sediments (n = 7) and coke-oven emissions sources (r = 0.69-0.78, n = 5), and between urban sediments (n = 22) and coal-tar-based sealcoat dust (r = 0.94, n = 47) suggesting that coal-tar-based sealcoat is an important urban PAH source in this watershed linked to residential and commercial/industrial land use. Copyright © 2013 Elsevier Ltd. All rights reserved.

Distribution and sources of polycyclic aromatic hydrocarbon (PAH) in marine environment of China

NASA Astrophysics Data System (ADS)

Zheng, Jinshu; Richardson, Bruce J.; Shouming, O.; Zheng, Jianhua

2004-06-01

Polycyclic aromatic hydrocarbons (PAHs) are potentially carcinogenic and mutagenic compounds that have raised considerable environmental concern. The highest concentrations of PAHs in the coastal sediment samples in China was 5.8 11.0μg/g (dry weight) in the core from the Huangpu River, Shanghai. The second highest concentration of PAHs was 4.42μg/g (dry weight) in surface sediment of Victoria Harbour in Hong Kong, and 5.73μg/g (dry weight) in sediment of Jiaozhou Bay, Qingdao City. The low concentrations of PAHs were always in the sediments far away from industrial zones and cities, and ranged from 0.10 to 0.30μg/g (dry weight). Several environmental parameters are considered for the identification of sources of PAHs in marine environment. High proportion of naphthalene, low molecular weight PAHs and alkylated PAHs, plus high ratio of phenanthrene to anthracene (>15) and low ratio of fluoranthene to pyrene (<1) suggested a petrogenic source. According to these parameters, the Changjiang (Yangtze) River estuary of Shanghai, Jiaozhou Bay of Qingdao City, Zhujiang (Pearl) River mouth, Jiulong River mouth and most of Hong Kong coastal waters were heavily contaminated by PAHs from petrogenic sources. However, PAHs in rural coastal areas were dominated by pyrolytic origin PAHs. This review clearly showed that oil pollution and incomplete combustion of oil, coal and biomass are the main reason for PAHs anormalies in the study areas.

BIODEGRADATION OF SEDIMENT-BOUND PAHS IN FIELD-CONTAMINATED SEDIMENT

EPA Science Inventory

The biodegradation of polycyclic aromatic hydrocarbons (PAHs) has been reported to occur under aerobic, sulfate reducing, and denitrifying conditions. PAHs present in contaminated sites, however, are known for their persistence. Most published studies were conducted in systems wh...

Mechanism-Based Classification of PAH Mixtures to Predict Carcinogenic Potential.

PubMed

Tilton, Susan C; Siddens, Lisbeth K; Krueger, Sharon K; Larkin, Andrew J; Löhr, Christiane V; Williams, David E; Baird, William M; Waters, Katrina M

2015-07-01

We have previously shown that relative potency factors and DNA adduct measurements are inadequate for predicting carcinogenicity of certain polycyclic aromatic hydrocarbons (PAHs) and PAH mixtures, particularly those that function through alternate pathways or exhibit greater promotional activity compared to benzo[a]pyrene (BaP). Therefore, we developed a pathway-based approach for classification of tumor outcome after dermal exposure to PAH/mixtures. FVB/N mice were exposed to dibenzo[def,p]chrysene (DBC), BaP, or environmental PAH mixtures (Mix 1-3) following a 2-stage initiation/promotion skin tumor protocol. Resulting tumor incidence could be categorized by carcinogenic potency as DBC > BaP = Mix2 = Mix3 > Mix1 = Control, based on statistical significance. Gene expression profiles measured in skin of mice collected 12 h post-initiation were compared with tumor outcome for identification of short-term bioactivity profiles. A Bayesian integration model was utilized to identify biological pathways predictive of PAH carcinogenic potential during initiation. Integration of probability matrices from four enriched pathways (P < .05) for DNA damage, apoptosis, response to chemical stimulus, and interferon gamma signaling resulted in the highest classification accuracy with leave-one-out cross validation. This pathway-driven approach was successfully utilized to distinguish early regulatory events during initiation prognostic for tumor outcome and provides proof-of-concept for using short-term initiation studies to classify carcinogenic potential of environmental PAH mixtures. These data further provide a 'source-to-outcome' model that could be used to predict PAH interactions during tumorigenesis and provide an example of how mode-of-action-based risk assessment could be employed for environmental PAH mixtures. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

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.

Heterogeneous ozonation reactions of PAHs and fatty acid methyl esters in biodiesel particulate matter

NASA Astrophysics Data System (ADS)

Kasumba, John; Holmén, Britt A.

2018-02-01

Numerous studies have examined the oxidation of PAHs found in diesel particulate matter (PM) by ozone, but no studies have investigated the ozone oxidation of biodiesel exhaust PM. Fatty acid methyl esters (FAMEs), found in high abundance in biodiesel PM, can potentially alter the kinetics of the reactions between atmospheric oxidants such as ozone and particle-phase PAHs. In this study, the heterogeneous reactivity of 16 EPA PAHs upon 24 h exposure to 0.4 ppm ozone in the presence (PAH + FAMES) and absence (PAH-only) of FAMEs was investigated at room temperature and 50% relative humidity. The ozone-reactivity of the PAHs detected in 20% biodiesel (B20) exhaust PM was also investigated. In the absence of FAMEs, the pseudo-first order ozone reaction rate constant, kO 3 , of PAHs varied from 0.086 ± 0.030 hr-1 (chrysene) to 0.184 ± 0.078 hr-1 (anthracene). In the presence of FAMEs, kO 3 of the PAHs varied between 0.013 ± 0.012 hr-1 (benzo[b]fluoranthene) and 0.168 ± 0.028 hr-1 (benzo[a]pyrene), and with the exception of benzo[a]pyrene, the kO 3 of PAHs were 1.2-8 times lower compared to those obtained during the PAH-only ozone exposure. Only one PAH, benzo[a]pyrene (BaP), did not show a significant change in kO3 with addition of FAMEs. Phenanthrene, fluoranthene, and pyrene, the only PAHs detected in the B20 PM, had kO 3 values about 4 times lower in B20 PM than those obtained when spiked PAHs-only were exposed to ozone. The kO 3 values of phenanthrene and fluoranthene in the B20 PM were 2 times higher than rates obtained when the PAH mix was exposed to ozone in the presence of the FAMEs. In contrast, pyrene's kO 3 in the B20 PM was about 2 times lower than that obtained for the PAH + FAMEs exposure. Observed differences in PAH behavior demonstrate individual PAH heterogeneous reactivity with gas-phase ozone is sensitive to PAH (vapor pressure, solubility/sorption to matrix components, chemical reactivity) as well as substrate properties (PAH and O3 diffusivity

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

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

Zhou, Hui; Energy Research Institute, University of Leeds, Leeds LS2 9JT; Wu, Chunfei, E-mail: c.wu@leeds.ac.uk

2015-02-15

Highlights: • PAH from pyrolysis of 9 MSW fractions was investigated. • Pyrolysis of plastics released more PAH than that of biomass. • Naphthalene was the most abundant PAH in the tar. • The mechanism of PAH release from biomass and plastics was proposed. - Abstract: The formation of 2–4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. Themore » results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock.« less

Impact of natural gas extraction on PAH levels in ambient air.

PubMed

Paulik, L Blair; Donald, Carey E; Smith, Brian W; Tidwell, Lane G; Hobbie, Kevin A; Kincl, Laurel; Haynes, Erin N; Anderson, Kim A

2015-04-21

Natural gas extraction, often referred to as "fracking," has increased rapidly in the U.S. in recent years. To address potential health impacts, passive air samplers were deployed in a rural community heavily affected by the natural gas boom. Samplers were analyzed for 62 polycyclic aromatic hydrocarbons (PAHs). Results were grouped based on distance from each sampler to the nearest active well. PAH levels were highest when samplers were closest to active wells. Additionally, PAH levels closest to natural gas activity were an order of magnitude higher than levels previously reported in rural areas. Sourcing ratios indicate that PAHs were predominantly petrogenic, suggesting that elevated PAH levels were influenced by direct releases from the earth. Quantitative human health risk assessment estimated the excess lifetime cancer risks associated with exposure to the measured PAHs. Closest to active wells, the risk estimated for maximum residential exposure was 2.9 in 10 000, which is above the U.S. EPA's acceptable risk level. Overall, risk estimates decreased 30% when comparing results from samplers closest to active wells to those farthest. This work suggests that natural gas extraction may be contributing significantly to PAHs in air, at levels that are relevant to human health.

Impact of natural gas extraction on Pah levels in ambient air

PubMed Central

Paulik, L. Blair; Donald, Carey E.; Smith, Brian W.; Tidwell, Lane G.; Hobbie, Kevin A.; Kincl, Laurel; Haynes, Erin N.; Anderson, Kim A.

2015-01-01

Natural gas extraction, often referred to as “fracking,” has increased rapidly in the U.S. in recent years. To address potential health impacts, passive air samplers were deployed in a rural community heavily affected by the natural gas boom. Samplers were analyzed for 62 polycyclic aromatic hydrocarbons (PAHs). Results were grouped based on distance from each sampler to the nearest active well. PAH levels were highest when samplers were closest to active wells. Additionally, PAH levels closest to natural gas activity were an order of magnitude higher than levels previously reported in rural areas. Sourcing ratios indicate that PAHs were predominantly petrogenic, suggesting that elevated PAH levels were influenced by direct releases from the earth. Quantitative human health risk assessment estimated the excess lifetime cancer risks associated with exposure to the measured PAHs. Closest to active wells, the risk estimated for maximum residential exposure was 2.9 in 10,000, which is above the U.S. EPA's acceptable risk level. Overall, risk estimates decreased 30% when comparing results from samplers closest to active wells to those farthest. This work suggests that natural gas extraction may be contributing significantly to PAHs in air, at levels that are relevant to human health. PMID:25810398

Airborne Measurements of atmospheric PAH's across Europe

NASA Astrophysics Data System (ADS)

Davison, B.; Jaward, F.; Jones, K.; Lee, R.

2003-04-01

Atmospheric measurements of PAHs were taken aboard the DRL Falcon 20 during May 2001. A sampling system was designed to work aboard this aircraft platform. Particulate PAHs were collected on a glass fiber filter (GFF) with their gaseous component concentrated on a polyurethane foam sheets located behind the filter. Typically sampling volumes of between 20-50m^3 were collected which equated to a collection time of about 30minutes. In this way the distance travelled was kept within an acceptable level, about 60 nautical miles. The average concentrations of the data set for phenanthrene was 450 pg m-3 while values for many of the heavier PAH marker compounds used in the UK such as benzo(a)pyrene, diben(ah)anthracene were below the detection limits on all flights. The results will be discussed with consideration of location, altitude and airmass trajectory.

BIOAVAILABILITY OF PAHS FROM PYROGENIC AND PETROGENIC SOURCES MEASURED USING GLASS FISH

EPA Science Inventory

Geochemical evidence indicates PAHs associated with pyrogenic sources behave differently than PAHs from petrogenic sources. There is also some evidence and supposition that PAHs from pyrogenic and petrogenic sources demonstrate differing bioavailability. In this study, we evaluat...

[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.

Emission and atmospheric transport of particulate PAHs in Northeast Asia.

PubMed

Inomata, Yayoi; Kajino, Mizuo; Sato, Keiichi; Ohara, Toshimasa; Kurokawa, Jun-Ichi; Ueda, Hiromasa; Tang, Ning; Hayakawa, Kazuichi; Ohizumi, Tsuyoshi; Akimoto, Hajime

2012-05-01

The emission, concentration levels, and transboundary transport of particulate polycyclic aromatic hydrocarbons (PAHs) in Northeast Asia were investigated using particulate PAH measurements, the newly developed emission inventory (Regional Emission inventory in ASia for Persistent Organic Pollutants version, REAS-POP), and the chemical transport model (Regional Air Quality Model ver2 for POPs version, RAQM2-POP). The simulated concentrations of the nine particulate PAHs agreed well with the measured concentrations, and the results firmly established the efficacy of REAS/RAQM2-POP. It was found that the PAH concentrations in Beijing (China, source region), which were emitted predominantly from domestic coal, domestic biofuel, and other transformations of coal (including coke production), were approximately 2 orders of magnitude greater than those monitored at Noto (Japan, leeward region). In Noto, the PAH concentrations showed seasonal variations; the PAH concentrations were high from winter to spring due to contributions from domestic coal, domestic biofuel, and other transformations of coal, and low in summer. In summer, these contribution were decrease, instead, other sources, such as the on-road mobile source, were relatively increased compared with those in winter. These seasonal variations were due to seasonal variations in emissions from China, as well as transboundary transport across the Asian continent associated with meteorological conditions. © 2012 American Chemical Society

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.

PAH Metabolites in Bile of European Eel (Anguilla anguilla) from Morocco.

PubMed

Wariaghli, Fatima; Kammann, Ulrike; Hanel, Reinhold; Yahyaoui, Ahmed

2015-12-01

Environmental pollution of fish with organic contaminants is a topic of rising attention in Morocco. Polycyclic aromatic hydrocarbons (PAH) are prominent organic contaminants which are rapidly metabolized in fish. Their metabolites are accumulated in the bile fluid and can be used to assess PAH exposure. The two PAH metabolites 1-hydroxypyrene and 1-hydroxyphenanthrene were quantified in European eels (Anguilla anguilla) from two Moroccan river systems by high-performance liquid chromatography with fluorescence detection. Mean values ranged from 52 to 210 ng/mL 1-hydroxypyrene and from 61 to 73 ng/mL 1-hydroxyphenanthrene. The overall concentrations of PAH metabolites in eel from Morocco appeared moderate compared to eel from European rivers and coastal sites. The present study provides first information on concentrations of PAH metabolites in fish from Morocco.

PAH emissions from old and new types of domestic hot water boilers.

PubMed

Horak, Jiri; Kubonova, Lenka; Krpec, Kamil; Hopan, Frantisek; Kubesa, Petr; Motyka, Oldrich; Laciok, Vendula; Dej, Milan; Ochodek, Tadeas; Placha, Daniela

2017-06-01

Five different domestic heating boilers (automatic, over-fire, with down-draft combustion and gasification) and three types of fuel (lignite, wood and mixed fuel) were examined in 25 combustion tests and correlated with the emissions of particulate matter (PM), carbon monoxide (CO), total organic carbon (TOC) and 12 polycyclic aromatic hydrocarbons (PAHs with MW = 178-278 g/mol) focusing on particle phase. However, the distribution of 12 PAHs in gas phase was considered as well due to the presence mainly of lighter PAHs in gas phase. The PAHs, as well as the CO and TOC, are the indicators of incomplete combustion, and in this study PAH emission increased significantly with increasing emissions of CO and TOC. The PAHs were mainly detected on PM 2.5 , their contents were increasing linearly with increasing PM 2.5 emissions. The highest emission factors of PAHs were measured for boilers of old construction, such as over-fire boiler (5.8-929 mg/kg) and boiler with down-draft combustion (3.1-54.1 mg/kg). Modern types of boilers produced much lower emissions of PAHs, in particular, automatic boiler (0.3-3.3 mg/kg) and gasification boilers (0.2-6.7 mg/kg). In general, the inefficient combustion at reduced output of boilers generated 1.4-17.7 times more emissions of PAHs than the combustion at nominal output of boilers. It is recommended to operate boilers at nominal output with sufficient air supply and to use the proper fuel to minimise PAHs emissions from domestic heating appliances. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparative survey of PAHs incidence in Portuguese traditional meat and blood sausages.

PubMed

Roseiro, L C; Gomes, A; Patarata, L; Santos, C

2012-06-01

Sixteen polycyclic aromatic hydrocarbons (PAHs) in representative traditional sausages produced in "Trás-os-Montes" and "Alentejo", were determined. Light PAHs represented similar overall contents in both regions and showed close decreasing order patterns (ACY, PHE, FLR and NAP), irrespective of the product type considered. Amongst the carcinogenic/mutagenic PAHs analyzed (PAH8), both regions also had greater contents associated to BaA and CHR, with slightly higher values for the former compound in "Alentejo" and, oppositely, for the later in "Trás-os-Montes". However, their quantitative comparison showed that the general mean total PAH content found in "Trás-os-Montes" was almost 3-fold higher than in similar products from "Alentejo" and this factor was about 8-fold superior when the PAH8 and PAH4 indicators were compared, expressing benzo[a]pyrene toxic equivalencies (BaPE), 15 times (total mean toxicity), 34 times (PAH8) and 9 times (PAH4) higher. In general terms, the mean BaP content of all analyzed samples from "Alentejo" was 0.41 μg kg(-1). Differently that value in "Trás-os-Montes" reached 3.57 μg kg(-1), expressing concerning average contents of 5.35, 5.87 and 4.51 μg kg(-1) in Chouriço de Carne, Moura and Salpicão sausages, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Remarkably constant PAH concentrations in Swiss soils over the last 30 years.

PubMed

Gubler, Andreas; Wächter, Daniel; Blum, Franziska; Bucheli, Thomas D

2015-10-01

Although polycyclic aromatic hydrocarbons (PAH) are of concern due to their carcinogenic, mutagenic, and teratogenic properties and their ubiquitous occurrence in environmental compartments, only few studies assessed the temporal evolutions of PAH contents of soils over extended time periods. The Swiss Soil Monitoring Network NABO runs long-term monitoring sites resampled every five years since the 1980s. In the present study, soil (0-20 cm) samples collected from 1985 through 2013 at 25 selected monitoring sites were analysed for the 16 priority PAH according to the U.S. EPA and five PAH marker substances. We observed divergent trends for light PAH, such as naphthalene and phenanthrene, compared with heavy PAH, such as benzo[a]pyrene and benzo[ghi]perylene. Whereas the former showed decreasing concentrations since the late 1980s, no significant trends were found for the latter. Furthermore, the analyses showed that naphthalene contents decreased most strongly at rural sites featuring low population densities, while phenanthrene contents generally decreased most strongly at semi-rural sites. The deviating evolutions of light and heavy PAH were mainly attributed to their differing physico-chemical properties. Temporal evolutions in soils contradict emission inventory data suggesting PAH emissions to decline since the 1980s.

Distribution, partition and removal of polycyclic aromatic hydrocarbons (PAHs) during coking wastewater treatment processes.

PubMed

Zhang, Wanhui; Wei, Chaohai; An, Guanfeng

2015-05-01

In this study, we report the performance of a full-scale conventional activated sludge (A-O1-O2) treatment in eliminating polycyclic aromatic hydrocarbons (PAHs). Both aqueous and solid phases along with the coking wastewater treatment processes were analyzed for the presence of 18 PAHs. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent and sludge samples. In the coking wastewater treatment system, 4-5 ring PAHs were the dominant compounds, while 4 rings PAHs predominated in the sludge samples. Over 98% of the PAH removal was achieved in the coking wastewater treatment plant (WWTP), with the total concentration of PAHs being 21.3 ± 1.9 μg L(-1) in the final effluent. During the coking wastewater treatment processes, the association of the lower molecular weight PAH with suspended solids was generally less than 60%, while the association of higher molecular weight PAHs was greater than 90%. High distribution efficiencies (Kdp and Kds) were found, suggesting that adsorption was the potential removal pathway of PAHs. Finally, the mass balances of PAHs in various stages of the coking WWTP were obtained, and the results indicated that adsorption to sludge was the main removal pathway for PAHs in the coking wastewater treatment processes.

Dry Deposition of Polycyclic Aromatic Hydrocarbons (PAHs) at a Suburban Site in Beijing, China

NASA Astrophysics Data System (ADS)

Zhang, Xincheng; Wang, Weiyu; Zhu, Xianlei

2017-04-01

A great amount of polycyclic aromatic hydrocarbons (PAHs) have been generated by industrial production, waste incineration and landfill, traffic and road dust etc. They are emitted into atmosphere and afterwards enter into water body and soil through deposition, resulting in wide distribution of PAHs in environment. However, the dry deposition of PAHs from atmosphere has not been well studied, especially in the aspects of its characteristics, environmental and health effects, sources and mechanism. This study measured PAHs dry deposition in the northwest suburban area of Beijing. Dry deposition samples (i.e. dustfall samples) were collected at the sampling site located in China University of Petroleum - Beijing in 2012-2016. And PAHs in the samples were determined by GC/MS. The dry deposition flux of 16 US EPA priority PAHs (ΣPAH16) was 2.58 μg/(m^2·d), which was lower than those in other regions of North China. Its seasonal variability was more significant than annual variability (p<0.05) and the seasonal pattern was winter > spring > autumn > summer. The amount of ΣPAH16 removed from the atmosphere by dry deposition process accounted for only 1.2% of their emissions, indicating that the atmosphere self-purification capacity was quite limited and emission reduction measures would play a key role in controlling PAHs air pollution. However, PAHs dry deposition would deteriorate soil quality since the content of ΣPAH16 in dustfall was 1-2 orders of magnitude higher than that in soil in the same area. Dermal exposure resulting from PAHs dry deposition was not the major route. The sources of PAHs dry deposition varied with seasons. The profile and specific ratios of PAHs showed that in winter, domestic coal combustion was the main source of PAHs with the contribution up to 77%; in spring and summer, the impact of coal combustion decreased and the contribution of vehicle exhaust increased to 30% - 45%; in fall, in addition to coal combustion and vehicle exhaust

Biomonitoring of PAHs by using Quercus ilex leaves: Source diagnostic and toxicity assessment

NASA Astrophysics Data System (ADS)

De Nicola, Flavia; Claudia, Lancellotti; MariaVittoria, Prati; Giulia, Maisto; Anna, Alfani

2011-03-01

Quercus ilex L. leaves were sampled at nineteen urban sites and two remote sites in order to evaluate PAH contamination degree. One-, two- and three-year-old leaves were collected and leaf lipid content was measured to investigate the influence of leaf age and lipids in PAH accumulation. Some PAH diagnostic ratios, such as Ant/Ant + Phen, Flt/Flt + Pyr, B[a]A/B[a]A + Crys and IP/IP + B[g,h,i]P, were calculated. The results suggest that Q. ilex leaves are effective biomonitors of PAH air contamination: in fact, a great PAH accumulation in leaves from the urban areas, until 30-time higher compared to those from the remote sites, has been observed. At each site, the similar total PAH concentrations in leaves of different age, probably due to a canopy effect, indicate an ability of all leaf age classes to monitor local PAH concentrations in air, remarking practical implications for air biomonitoring. The findings suggest that PAH adsorption in Q. ilex leaves does not result limited by leaf lipid content. Moreover, this study demonstrates the source-diagnostic potential of Q. ilex leaves, because, in particular, the Flt/Flt + Pyr and IP/IP + B[g,h,i]P ratios indicate vehicular traffic as the main source of PAHs in the urban areas and wood combustion in the remote areas. Moreover, to distinguish biomass combustion source, a promising tracer PAH as DB[a,h]A could be used. The high contribution of DB[a,h]A to total PAH concentrations at the remote sites determines a high carcinogenic potential in this area, similar to that calculated for the urban area where the carcinogenic PAH concentrations in absolute values are often higher.

Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

NASA Astrophysics Data System (ADS)

Sheesley, R. J.; Kruså, M.; Krecl, P.; Johansson, C.; Gustafsson, Ã.-.

2009-05-01

Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycyclic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC) means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from -138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution, which was constrained to 71-87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an fbiomass of 71%, while fluoranthene and phenanthrene (gas phase) had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.

Particle-scale measurement of PAH aqueous equilibrium partitioning in impacted sediments.

PubMed

Ghosh, Upal; Hawthorne, Steven B

2010-02-15

This research investigated the particle-scale processes that control aqueous equilibrium partitioning of PAHs in manufactured gas plant (MGP) site sediments. Dominant particle types in impacted sediments (sand, wood, coal/coke, and pitch) were physically separated under a microscope for equilibrium assessments. Solid-phase microextraction (SPME) combined with selected ion monitoring GC/MS and perdeuterated PAH internal standards were used to determine freely dissolved PAH concentrations in small (0.1-1 mL) water samples at concentrations as low as microg/L (for lower molecular weight PAHs) to ng/L (for higher molecular weight PAHs). For every particle class the initial release of PAHs into the aqueous phase was rapid, and an apparent equilibrium was reached in a matter of days. The average ratio of aqueous total PAH concentration for pitch vs coal/coke particles for eight sediment samples was 20. Thus, sediments that had aged in the field for many decades were not at equilibrium and were still going through a slow process of contaminant mass transfer between the different particle types. A possible consequence of this slow aging process is further lowering of the activity of the chemical as mass transfer is achieved to new sorption sites with time. This study also found that the presence of black carbon even at the level of (1)/(3) of sediment organic carbon does not necessarily imply a BC-dominated sorption behavior, rather source pitch particles if present may dominate PAH partitioning. To our knowledge this is the first report of equilibrium partitioning assessment conducted at the sediment particle scale.

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.

Impact of clay mineral, wood sawdust or root organic matter on the bacterial and fungal community structures in two aged PAH-contaminated soils.

PubMed

Cébron, Aurélie; Beguiristain, Thierry; Bongoua-Devisme, Jeanne; Denonfoux, Jérémie; Faure, Pierre; Lorgeoux, Catherine; Ouvrard, Stéphanie; Parisot, Nicolas; Peyret, Pierre; Leyval, Corinne

2015-09-01

The high organic pollutant concentration of aged polycyclic aromatic hydrocarbon (PAH)-contaminated wasteland soils is highly recalcitrant to biodegradation due to its very low bioavailability. In such soils, the microbial community is well adapted to the pollution, but the microbial activity is limited by nutrient availability. Management strategies could be applied to modify the soil microbial functioning as well as the PAH contamination through various amendment types. The impact of amendment with clay minerals (montmorillonite), wood sawdust and organic matter plant roots on microbial community structure was investigated on two aged PAH-contaminated soils both in laboratory and 1-year on-site pot experiments. Total PAH content (sum of 16 PAHs of the US-EPA list) and polar polycyclic aromatic compounds (pPAC) were monitored as well as the available PAH fraction using the Tenax method. The bacterial and fungal community structures were monitored using fingerprinting thermal gradient gel electrophoresis (TTGE) method. The abundance of bacteria (16S rRNA genes), fungi (18S rRNA genes) and PAH degraders (PAH-ring hydroxylating dioxygenase and catechol dioxygenase genes) was followed through qPCR assays. Although the treatments did not modify the total and available PAH content, the microbial community density, structure and the PAH degradation potential changed when fresh organic matter was provided as sawdust and under rhizosphere influence, while the clay mineral only increased the percentage of catechol-1,2-dioxygenase genes. The abundance of bacteria and fungi and the percentage of fungi relative to bacteria were enhanced in soil samples supplemented with wood sawdust and in the plant rhizospheric soils. Two distinct fungal populations developed in the two soils supplemented with sawdust, i.e. fungi related to Chaetomium and Neurospora genera and Brachyconidiellopsis and Pseudallescheria genera, in H and NM soils respectively. Wood sawdust amendment favoured the

Host Pah1p phosphatidate phosphatase limits viral replication by regulating phospholipid synthesis

PubMed Central

Zhang, Zhenlu; He, Guijuan; Catanzaro, Nicholas; Wu, Zujian; Xie, Lianhui

2018-01-01

Replication of positive-strand RNA viruses [(+)RNA viruses] takes place in membrane-bound viral replication complexes (VRCs). Formation of VRCs requires virus-mediated manipulation of cellular lipid synthesis. Here, we report significantly enhanced brome mosaic virus (BMV) replication and much improved cell growth in yeast cells lacking PAH1 (pah1Δ), the sole yeast ortholog of human LIPIN genes. PAH1 encodes Pah1p (phosphatidic acid phosphohydrolase), which converts phosphatidate (PA) to diacylglycerol that is subsequently used for the synthesis of the storage lipid triacylglycerol. Inactivation of Pah1p leads to altered lipid composition, including high levels of PA, total phospholipids, ergosterol ester, and free fatty acids, as well as expansion of the nuclear membrane. In pah1Δ cells, BMV replication protein 1a and double-stranded RNA localized to the extended nuclear membrane, there was a significant increase in the number of VRCs formed, and BMV genomic replication increased by 2-fold compared to wild-type cells. In another yeast mutant that lacks both PAH1 and DGK1 (encodes diacylglycerol kinase converting diacylglycerol to PA), which has a normal nuclear membrane but maintains similar lipid compositional changes as in pah1Δ cells, BMV replicated as efficiently as in pah1Δ cells, suggesting that the altered lipid composition was responsible for the enhanced BMV replication. We further showed that increased levels of total phospholipids play an important role because the enhanced BMV replication required active synthesis of phosphatidylcholine, the major membrane phospholipid. Moreover, overexpression of a phosphatidylcholine synthesis gene (CHO2) promoted BMV replication. Conversely, overexpression of PAH1 or plant PAH1 orthologs inhibited BMV replication in yeast or Nicotiana benthamiana plants. Competing with its host for limited resources, BMV inhibited host growth, which was markedly alleviated in pah1Δ cells. Our work suggests that Pah1p promotes

Source apportionment of atmospheric polycyclic aromatic hydrocarbons (PAHs) in Palm Beach County, Florida.

PubMed

Afshar-Mohajer, Nima; Wilson, Christina; Wu, Chang-Yu; Stormer, James E

2016-04-01

Due to concerns about adverse health effects associated with inhalation of atmospheric polycyclic aromatic hydrocarbons (PAHs), 30 ambient air samples were obtained at an air quality monitoring station in Palm Beach County, Florida, from March 2013 to March 2014. The ambient PAH concentration measurements and fractional emission rates of known sources were incorporated into a chemical mass balance model, CMB8.2, developed by EPA, to apportion contributions of three major PAH sources including preharvest sugarcane burning, mobile vehicles, and wildland fires. Strong association between the number of benzene rings and source contribution was found, and mobile vehicles were identified to be the prevailing source (contribution≥56%) for the observed PAHs concentration with lower molecular weights (four or fewer benzene rings) throughout the year. Preharvest sugarcane burning was the primary contributing source for PAHs with relatively higher molecular weights (five or more benzene rings) during the sugarcane burning season (from October to May of the next year). Source contribution of wildland fires varied among PAH compounds but was consistently lower than for sugarcane burning during the sugarcane harvest season. Determining the major sources responsible for ground-level PAHs serves as a tool to improving management strategies for PAH emitting sources and a step toward better protection of the health of residents in terms of exposure to PAHs. The results obtain insight into temporal dominance of PAH polluting sources for those residential areas located near sugarcane burning facilities and have implications beyond Palm Beach County, in areas with high concerns of PAHs and their linked sources. Source apportionment of atmospheric polycyclic hydrocarbons (PAHs) in Palm Beach County, Florida, meant to estimate contributions of major sources in PAH concentrations measured at Belle Glade City of Palm Beach County. Number of benzene rings was found to be the key parameter

Polycyclic aromatic hydrocarbon optical properties and contribution to the acceleration of stellar outflows

NASA Technical Reports Server (NTRS)

Cherchneff, Isabelle; Barker, John R.; Tielens, Alexander G. G. M.

1991-01-01

The optical constants of four polycyclic aromatic hydrocarbon (PAH) molecules (benzene, pyrene, pentacene, and coronene) are determined from their measured laboratory absorption spectra. The Planck mean of the radiation pressure cross section is computed for each molecule and for amorphous carbon (AC) grains, and semiempirically estimated for large PAH molecules up to 400 carbon atoms. Assuming that PAHs are present in carbon-rich stellar outflows, the radiation pressure forces acting on them are calculated and compared with the radiation forces on AC particles. The results show that PAHs possess very different optical properties from AC grains. Small PAHs may experience an 'inverse greenhouse' effect in the inner part of the envelope, as they decouple from the gas close to the photosphere. The radiation pressure force on PAHs is always much less than the force at work on AC grains, and PAH molecules do not affect significantly the dynamics of the outflow.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

DOE PAGES

Geier, Mitra C.; James Minick, D.; Truong, Lisa; ...

2018-04-01

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish.

PubMed

Geier, Mitra C; James Minick, D; Truong, Lisa; Tilton, Susan; Pande, Paritosh; Anderson, Kim A; Teeguardan, Justin; Tanguay, Robert L

2018-04-06

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. We constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilization (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

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

Geier, Mitra C.; James Minick, D.; Truong, Lisa

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these

PAHs sensitivity of picophytoplankton populations in the Red Sea.

PubMed

Kottuparambil, Sreejith; Agusti, Susana

2018-04-25

In this study, we investigated the in situ responses of Red Sea picophytoplankton, the dominant phytoplankton group in the oligotrophic ocean, to two toxic polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene. The experiments were conducted across a latitudinal gradient of the Saudi Arabian Red Sea, an area sensitive to oil pollution. We observed significant adverse effects on the growth and abundance of the picocyanobacteria Synechococcus and picoeukaryotes, at all stations sampled. Prochlorococcus, which was abundant only at one of the stations, also appeared to be affected. Pyrene was found to be more toxic to phytoplankton at all stations. In general, picoeukaryotes exhibited higher sensitivity to PAHs than Synechococcus. Populations in the highly oligotrophic Northern region of the Red Sea were more tolerant to PAHs, presumably influenced by the natural selection of more resistant strains of phytoplankton due to the prolonged exposure to PAHs. Toxicity threshold values estimated here are higher than those reported for picophytoplankton from other oligotrophic marine waters and exceed by far the natural levels of PAHs in many oceans. Our findings reveal a possible adaptation of picophytoplankton populations to oil-related contaminants, which may clearly influence their spatial distribution patterns in the Red Sea. Copyright © 2018 Elsevier Ltd. All rights reserved.

PAHs soil decontamination in two steps: desorption and electrochemical treatment.

PubMed

Alcántara, M Teresa; Gómez, Jose; Pazos, Marta; Sanromán, M Angeles

2009-07-15

The presence of carcinogenic polycyclic aromatic hydrocarbons (PAHs) in soils poses a potential threat to human health if exposure levels are too high. Nevertheless, the removal of these contaminants presents a challenge to scientists and engineers. The high hydrophobic nature of PAHs enables their strong sorption onto soil or sediments. Thus, the use of surfactants could favour the release of sorbed hydrophobic organic compounds from contaminated soils. In this work, five surfactants, namely Brij 35, Tergitol NP10, Tween 20, Tween 80 and Tyloxapol, are evaluated on the desorption of PAHs [benzanthracene (BzA), fluoranthene (FLU), and pyrene (PYR), single and in mixture] from a model sample such as kaolin. In all cases, the best results were obtained when Tween 80 was employed. In order to obtain the global decontamination of PAHs, their electrochemical degradation is investigated. It is concluded that the order of increasing degradation for single compounds is BzA>FLU>PYR when they are subject to the same electrochemical treatment. In addition, there is a direct relationship between the ionization potential and the electrochemical degradation of PAH.

AN OVERVIEW OF PARTITIONING AND BIOAVAILABILITY OF PAHS IN SEDIMENTS AND SOILS

EPA Science Inventory

Understanding and predicting any adverse effects of PAHs depends on generating a reliable measure or estimate of how much PAH is available for uptake. Simply knowing the total amount of PAH in soil, water or sediment is insufficient for determining whether or not these compounds ...

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons in the 3 μm region: role of hydrogenation and alkylation

NASA Astrophysics Data System (ADS)

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

2018-03-01

Aim. We aim to elucidate the spectral changes in the 3 μm region that result from chemical changes in the molecular periphery of polycyclic aromatic hydrocarbons (PAHs) with extra hydrogens (H-PAHs) and methyl groups (Me-PAHs). Methods: Advanced laser spectroscopic techniques combined with mass spectrometry were applied on supersonically cooled 1,2,3,4-tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, 1,2,3,6,7,8-hexahydropyrene, 9-methylanthracene, and 9,10-dimethylanthracene, allowing us to record mass-selective and conformationally selective absorption spectra of the aromatic, aliphatic, and alkyl CH-stretches in the 3.175 - 3.636 µm region with laser-limited resolution. We compared the experimental absorption spectra with standard harmonic calculations and with second-order vibrational perturbation theory anharmonic calculations that use the SPECTRO program for treating resonances. Results: We show that anharmonicity plays an important if not dominant role, affecting not only aromatic, but also aliphatic and alkyl CH-stretch vibrations. The experimental high-resolution data lead to the conclusion that the variation in Me- and H-PAHs composition might well account for the observed variations in the 3 μm emission spectra of carbon-rich and star-forming regions. Our laboratory studies also suggest that heavily hydrogenated PAHs form a significant fraction of the carriers of IR emission in regions in which an anomalously strong 3 μm plateau is observed.

PAH dissipation in spiked soil: impacts of bioavailability, microbial activity, and trees.

PubMed

Mueller, Kevin E; Shann, Jodi R

2006-08-01

While trees have demonstrated potential in phytoremediation of several organic contaminants, little is known regarding their ability to impact the common soil contaminant PAHs. Several species of native North American trees were planted in soil artificially contaminated with three PAHs. Plant biomass, PAH dissipation, and microbial mineralization were monitored over the course of one year and environmental conditions were allowed to follow typical seasonal patterns. PAH dissipation and mineralization were not affected by planting. Extensive and rapid loss of PAHs was observed and attributed to high bioavailability and microbial activity in all treatments. The rate of this loss may have masked any significant planting effects. Anthracene was found to be more recalcitrant than pyrene or phenanthrene. Parallel soil aging studies indicated that sequestration to soil components was minimal. Contrary to common inferences in literature, amendment with decaying fine roots inhibited PAH degradation by the soil microbial community. Seasonal variation in environmental factors and rhizosphere dynamics may have also reduced or negated the effect of planting and should be taken into account in future phytoremediation trials. The unique root traits of trees may pose a challenge to traditional thought regarding PAH dissipation in the rhizosphere of plants.

Enrichment behavior and transport mechanism of soil-bound PAHs during rainfall-runoff events.

PubMed

Zheng, Yi; Luo, Xiaolin; Zhang, Wei; Wu, Bin; Han, Feng; Lin, Zhongrong; Wang, Xuejun

2012-12-01

Polycyclic Aromatic Hydrocarbons (PAHs) transported by surface runoff result in nonpoint source pollution and jeopardize aquatic ecosystems. The transport mechanism of PAHs during rainfall-runoff events has been rarely studied regarding pervious areas. An experimental system was setup to simulate the runoff pollution process on PAHs-contaminated soil. The enrichment behavior of soil-bound PAHs was investigated. The results show that soil organic matters (SOM), rather than clay particles, seem to be the main carrier of PAHs. The enrichment is highly conditioned on runoff and erosion processes, and its magnitude varies among PAH compounds. It is not feasible to build a simple and universal relationship between enrichment ratio and sediment discharge following the traditional enrichment theory. To estimate the flux of PAHs from pervious areas, soil erosion process has to be clearly understood, and both organic carbon content and composition of SOM should be factored into the calculation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

NASA Astrophysics Data System (ADS)

Sheesley, R. J.; Kruså, M.; Krecl, P.; Johansson, C.; Gustafsson, Ã.-.

2008-12-01

Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycylic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in residential wood combustion means than this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from -138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution that was constrained to a range of 71% for indeno[cd]pyrene+benzo[ghi]perylene to 87% for the gas phase phenanthrene and particulate fluoranthene, respectively. Indeno[cd]pyrene plus benzo[ghi]perylene, known to be enhanced in gasoline-powered motor vehicle exhaust compared to diesel exhaust, had the lowest contribution of biomass combustion of the measured PAHs by 9%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs demonstrate the non-uniformity of biomass combustion contribution to different PAHs even in a location with limited local emission sources and illustrates that regulatory efforts would not evenly reduce all PAHs.

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

Polycyclic aromatic hydrocarbons and PAH-related DNA adducts.

PubMed

Ewa, Błaszczyk; Danuta, Mielżyńska-Švach

2017-08-01

Investigations on the impact of chemicals on the environment and human health have led to the development of an exposome concept. The exposome refers to the totality of exposures received by a person during life, including exposures to life-style factors, from the prenatal period to death. The exposure to genotoxic chemicals and their reactive metabolites can induce chemical modifications of DNA, such as, for example, DNA adducts, which have been extensively studied and which play a key role in chemically induced carcinogenesis. Development of different methods for the identification of DNA adducts has led to adopting DNA adductomic approaches. The ability to simultaneously detect multiple PAH-derived DNA adducts may allow for the improved assessment of exposure, and offer a mechanistic insight into the carcinogenic process following exposure to PAH mixtures. The major advantage of measuring chemical-specific DNA adducts is the assessment of a biologically effective dose. This review provides information about the occurrence of the polycyclic aromatic hydrocarbons (PAHs) and their influence on human exposure and biological effects, including PAH-derived DNA adduct formation and repair processes. Selected methods used for determination of DNA adducts have been presented.

PAHs in leachates from thermal power plant wastes and ash-based construction materials.

PubMed

Irha, Natalya; Reinik, Janek; Jefimova, Jekaterina; Koroljova, Arina; Raado, Lembi-Merike; Hain, Tiina; Uibu, Mai; Kuusik, Rein

2015-08-01

The focus of the current study is to characterise the leaching behaviour of polycyclic aromatic hydrocarbons (PAHs) from oil shale ashes (OSAs) of pulverised firing (PF) and circulating fluidised-bed (CFB) boilers from Estonian Thermal Power Plant (Estonia) as well as from mortars and concrete based on OSAs. The target substances were 16 PAHs from the EPA priority pollutant list. OSA samples and OSA-based mortars were tested for leaching, according to European standard EN 12457-2 (2002). European standard CEN/TC 15862(2012) for monolithic matter was used for OSA-based concrete. Water extracts were analysed by GC-MS for the concentration of PAHs. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene were detected. Still, the release of PAHs was below the threshold limit value for inert waste. The amount of the finest fraction (particle size <0.045 mm), the content of the Al-Si glass phase and the surface characteristics were the main factors, which could affect the accessibility of PAHs for leaching. The mobility of PAHs from OSA of CFB and PF boilers was 20.2 and 9.9%, respectively. Hardening of OSA-based materials did not lead to the immobilisation of soluble PAHs. Release of PAHs from the monolith samples did not exceed 0.5 μg/m(2). In terms of leaching of PAHs, OSA is safe to be used for construction purposes.

Anaerobic biodegradation of PAHs in mangrove sediment with amendment of NaHCO3.

PubMed

Li, Chun-Hua; Wong, Yuk-Shan; Wang, Hong-Yuan; Tam, Nora Fung-Yee

2015-04-01

Mangrove sediment is unique in chemical and biological properties. Many of them suffer polycyclic aromatic hydrocarbon (PAH) contamination. However, the study on PAH biological remediation for mangrove sediment is deficient. Enriched PAH-degrading microbial consortium and electron acceptor amendment are considered as two effective measures. Compared to other electron acceptors, the study on CO2, which is used by methanogens, is still seldom. This study investigated the effect of NaHCO3 amendment on the anaerobic biodegradation of four mixed PAHs, namely fluorene (Fl), phenanthrene (Phe), fluoranthene (Flua) and pyrene (Pyr), with or without enriched PAH-degrading microbial consortium in mangrove sediment slurry. The trends of various parameters, including PAH concentrations, microbial population size, electron-transport system activities, electron acceptor and anaerobic gas production were monitored. The results revealed that the inoculation of enriched PAH-degrading consortium had a significant effect with half lives shortened by 7-13 days for 3-ring PAHs and 11-24 days for 4-ring PAHs. While NaHCO3 amendment did not have a significant effect on the biodegradation of PAHs and other parameters, except that CO2 gas in the headspace of experimental flasks was increased. One of the possible reasons is that mangrove sediment contains high concentrations of other electron acceptors which are easier to be utilized by anaerobic bacteria, the other one is that the anaerobes in mangrove sediment can produce enough CO2 gas even without adding NaHCO3. Copyright © 2015. Published by Elsevier B.V.

Sources and potential health risk of gas phase PAHs in Hexi Corridor, Northwest China.

PubMed

Mao, Xiaoxuan; Yu, Zhousuo; Ding, Zhongyuan; Huang, Tao; Ma, Jianmin; Zhang, Gan; Li, Jun; Gao, Hong

2016-02-01

Gas phase polycyclic aromatic hydrocarbons (PAHs) in Hexi Corridor, Northwest China were determined during heating and non-heating seasons, respectively, using passive air samplers. Polyurethane foam (PUF) disks were chosen as the sampling medium. Fifteen PAHs out of the 16 PAHs classified by the United States Environmental Protection Agency (U.S. EPA) were detected in this field sampling investigation. The atmospheric levels of sampled PAHs were higher at urban sites than that at rural sites among 14 sampling sites and increased during heating season. The highest concentration (11.34 ng m(-3)) was observed in Lanzhou during the heating season, the capital and largest industrial city of Gansu Province. PAH contamination in air was dominated by three aromatic ring congeners. Possible sources of PAHs were apportioned using PAH species ratios and the principle component analysis (PCA) combined with a multiple linear regression (MLR) method. Fossil fuel consumption was identified to be the predominant source of PAHs over Hexi Corridor, accounting for 43 % of the concentration of total (15) PAHs. Backward and forward trajectory and cluster analysis were also carried out to identify potential origins of PAHs monitored at several urban and rural sites. Lung cancer risk of local residents to gas phase PAHs via inhalation exposure throughout the province was found to be around a critical value of the lung cancer risk level at 10(-6) recommended by the U.S. EPA risk assessment guideline.

Current State of Knowledge in Microbial Degradation of Polycyclic Aromatic Hydrocarbons (PAHs): A Review

PubMed Central

Ghosal, Debajyoti; Ghosh, Shreya; Dutta, Tapan K.; Ahn, Youngho

2016-01-01

Polycyclic aromatic hydrocarbons (PAHs) include a group of organic priority pollutants of critical environmental and public health concern due to their toxic, genotoxic, mutagenic and/or carcinogenic properties and their ubiquitous occurrence as well as recalcitrance. The increased awareness of their various adverse effects on ecosystem and human health has led to a dramatic increase in research aimed toward removing PAHs from the environment. PAHs may undergo adsorption, volatilization, photolysis, and chemical oxidation, although transformation by microorganisms is the major neutralization process of PAH-contaminated sites in an ecologically accepted manner. Microbial degradation of PAHs depends on various environmental conditions, such as nutrients, number and kind of the microorganisms, nature as well as chemical property of the PAH being degraded. A wide variety of bacterial, fungal and algal species have the potential to degrade/transform PAHs, among which bacteria and fungi mediated degradation has been studied most extensively. In last few decades microbial community analysis, biochemical pathway for PAHs degradation, gene organization, enzyme system, genetic regulation for PAH degradation have been explored in great detail. Although, xenobiotic-degrading microorganisms have incredible potential to restore contaminated environments inexpensively yet effectively, but new advancements are required to make such microbes effective and more powerful in removing those compounds, which were once thought to be recalcitrant. Recent analytical chemistry and genetic engineering tools might help to improve the efficiency of degradation of PAHs by microorganisms, and minimize uncertainties of successful bioremediation. However, appropriate implementation of the potential of naturally occurring microorganisms for field bioremediation could be considerably enhanced by optimizing certain factors such as bioavailability, adsorption and mass transfer of PAHs. The main

Phototransformation rate constants of PAHs associated with soot particles.

PubMed

Kim, Daekyun; Young, Thomas M; Anastasio, Cort

2013-01-15

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k(p)(0)), the effective diffusion coefficients (D(eff)), and the light penetration depths (z(0.5)) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z(0.5) is more sensitive to the soot layer thickness than the k(p)(0) value. As the thickness of the soot layer increases, the z(0.5) values increase, but the k(p)(0) values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k(p)(0) and z(0.5) in thinner layers, D(eff) should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. Copyright © 2012 Elsevier B.V. All rights reserved.

Phototransformation Rate Constants of PAHs Associated with Soot Particles

PubMed Central

Kim, Daekyun; Young, Thomas M.; Anastasio, Cort

2013-01-01

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k0p), the effective diffusion coefficients (Deff), and the light penetration depths (z0.5) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z0.5 is more sensitive to the soot layer thickness than the k0p value. As the thickness of the soot layer increases, the z0.5 values increase, but the k0p values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k0p and z0.5 in thinner layers, Deff should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. PMID:23247292

Global time trends in PAH emissions from motor vehicles

PubMed Central

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

2013-01-01

Emission from motor vehicles is the most important source of polycyclic aromatic hydrocarbons (PAHs) in urban areas. Emission factors of individual PAHs for motor vehicles reported in the literature varied 4 to 5 orders of magnitude, leading to high uncertainty in emission inventory. In this study, key factors affecting emission factors of PAHs (EFPAH) for motor vehicles were evaluated quantitatively based on thousands of EFPAH measured in 16 countries for over 50 years. The result was used to develop a global emission inventory of PAHs from motor vehicles. It was found that country and vehicle model year are the most important factors affecting EFPAH, which can be quantified using a monovariate regression model with per capita gross domestic production (purchasing power parity) as a sole independent variable. On average, 29% of variation in log-transformed EFPAH could be explained by the model, which was equivalent to 90% reduction in overall uncertainty on arithmetic scale. The model was used to predict EFPAH and subsequently PAH emissions from motor vehicles for various countries in the world during a period from 1971 to 2030. It was estimated that the global emission reached its peak value of approximate 101 Gg in 1978 and decreased afterwards due to emission control in developed countries. The annual emission picked up again since 1990 owing to accelerated energy consumption in China and other developing countries. With more and more rigid control measures taken in the developing world, global emission of PAHs is currently passing its second peak. It was predicted that the emission would decrease from 77 Gg in 2010 to 42 Gg in 2030. PMID:24198716

[Internal Exposure Levels of PAHs of Primary School Students in Guangzhou].

PubMed

Su, Hui; Zhao, Bo; Zhang, Su-kun; Liu, Shan; Ren, Ming-zhong; Li, Jie; Shi, Xiao-xia

2015-12-01

In order to investigate the internal exposure levels of polycyclic aromatic hydrocarbons (PAHs) in primary school students of Guangzhou, the research collected urine of 78 and 86 primary school students from two primary schools in the summer of 2014, one school located in the ordinary residential area and the other in the industrial area. The contents of 10 kinds of OH-PAHs were tested by the rapid liquid chromatography coupled to triple quadruple tandem mass spectrometry. The results showed that the concentrations of total OH-PAHs in primary school students in the residential zone ranged from 0.83 µmol · mol⁻¹ to 80.63 µmol · mol⁻¹, while those in industrial area ranged from 1.06 µmol · mol⁻¹ to 72.47 µmol · mol⁻¹. The geometric average concentrations were 6.18 µmol · mol⁻¹ and 6.47 µmol · mol⁻¹, respectively, and there was no statistical significance between them (P > 0.05). Comparison of the exposure levels of different components of PAHs in the two areas found that all the OH-PAHs had no significant difference except for the levels of 1- OHP (P < 0.05). We should also pay attention to the higher exposure levels of PAHs in both areas when compared with other researches. In addition, the OH-PAHs in primary school students in the ordinary residential area had a good correlation between 0. 511 and 0.928 (P < 0.01), whereas there was no correlation between 1-OHP and 2-OHN, 1-OHN in the primary school students in the industrial area and other OH-PAHs had relatively weak correlation ranging from 0.338 to 0.855 (P < 0.01). This difference might indicate different pollution sources of PAHs in different functional areas, which was relatively single in the residential area, while the industrial area was polluted by multiple sources of industrial enterprises and logistics transportation emissions.

Effects of profession on urinary PAH metabolite levels in the US population.

PubMed

Liu, Bian; Jia, Chunrong

2016-01-01

Although exposure to polycyclic aromatic hydrocarbons (PAHs) is common in both environmental and occupational settings, few studies have compared PAH exposure among people with different professions. The purpose of this study was to investigate the variations in recent PAH exposure among different occupational groups over time using national representative samples. The study population consisted of 4162 participants from the 2001 to 2008 National Health and Nutrition Examination Survey, who had both urinary PAH metabolites and occupational information. Four corresponding monohydroxy-PAH urine metabolites: naphthalene (NAP), fluorene (FLUO), phenanthrene (PHEN), and pyrene (PYR) among seven broad occupational groups were analyzed using weighted linear regression models, adjusting for creatinine levels, sociodemographic factors, smoking status, and sampling season. The overall geometric mean concentrations of NAP, FLUO, PHEN, and PYR were 6927, 477, 335, and 87 ng/L, respectively. All four PAH metabolites were elevated in the "extractive, construction, and repair (ECR)" group, with 21-42 % higher concentrations than those in the reference group of "management." Similar trends were seen in the "operators, fabricators, and laborers (OFL)" group for FLUO, PHEN, and PYR. In addition, both "service" and "support" groups had elevated FLUO. Significant (p < 0.001) upward temporal trends were seen in NAP and PYR, with an approximately 6-17 % annual increase, and FLUO and PHEN remained relatively stable. Race and socioeconomic status show independent effects on PAH exposure. Heterogeneous distributions of urinary PAH metabolites among people with different job categories exist at the population level. The upward temporal trends in NAP and PYR warrant reduction in PAH exposure, especially among those with OFL and ECR occupations.

Electronic Spectroscopy of Trapped PAH Photofragments

NASA Astrophysics Data System (ADS)

Joblin, Christine; Bonnamy, Anthony

2016-06-01

The PIRENEA set-up combines an ion cyclotron resonance cell mass spectrometer with cryogenic cooling in order to study the physical and chemical properties of polycyclic aromatic hydrocarbons (PAHs) of astrophysical interest. In space, PAHs are submitted to UV photons that lead to their dissociation. It is therefore of interest to study fragmentation pathways and search for species that might be good interstellar candidates because of their stability. Electronic spectroscopy can bring major insights into the structure of species formed by photofragmentation. This is also a way to identify new species in space as recently illustrated in the case of C60^+. In PIRENEA, the trapped ions are not cold enough, and thus we cannot use complexation with rare gas in order to record spectroscopy, as was nicely performed in the work by Campbell et al. on C60^+. We are therefore using the dissociation of the trapped ions themselves instead, which requires in general a multiple photon scheme. This leads to non-linear effects that affect the measured spectrum. We are working on improving this scheme in the specific case of the photofragment obtained by H-loss from 1-methylpyrene cation (CH_3-C16H9^+). A recent theoretical study has shown that a rearrangement can occur from 1-pyrenemethylium cation (CH_2-C16H9^+) to a system containing a seven membered ring (tropylium like pyrene system). This study also reports the calculated electronic spectra of both isomers, which are specific enough to distinguish them, and as a function of temperature. We will present experiments that have been performed to study the photophysics of these ions using the PIRENEA set-up and a two-laser scheme for the action spectroscopy. J. Montillaud, C. Joblin, D. Toublanc, Astron. & Astrophys. 552 (2013), id.A15 E.K. Campbell, M. Holz, D. Gerlich, and J.P. Maier, Nature 523 (2015), 322-323 F. Useli-Bacchitta, A. Bonnamy, G. Malloci, et al., Chem. Phys. 371 (2010), 16-23; J. Zhen, A. Bonnamy, G. Mulas, C

25 years monitoring of PAHs and petroleum hydrocarbons biodegradation in soil.

PubMed

Harmsen, Joop; Rietra, René P J J

2018-05-10

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPH) in sediment and soil has been monitored on seven experimental fields during periods up to 25 years. With this unique dataset, we investigated long-term very slow biodegradation under field conditions. . The data show that three biodegradation rates can be distinguished for PAHs: 1) rapid degradation during the first year, 2) slow degradation during the following 6 years and 3), subject of this paper, a very slow degradation after 7 years until at least 25 years. Beside 2-, 3- and 4-ring PAHs, also 5- and 6-ring PAHs (aromatic rings) were degraded, all at the same rate during very slow degradation. In the period of very slow degradation, 6% yr -1 of the PAHs present were removed in five fields and 2% yr -1 in two other fields, while in the same period no very slow degradation of TPH could be observed. The remaining petroleum hydrocarbons were high boiling and non-toxic. Using the calculated degradation rates and the independently measured bioavailability of the PAHs (Tenax-method), the PAHs degradation curves of all seven monitored fields could be modelled. Applying the model and data obtained with the Tenax-method for fresh contaminated material, results of long-term biodegradation can be predicted, which can support the use of bioremediation in order to obtain a legally acceptable residual concentration. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Simulation of atmospheric PAH emissions from diesel engines.

PubMed

Durán, A; de Lucas, A; Carmona, M; Ballesteros, R

2001-08-01

Simulation of atmospheric PAH emissions in a typical European passenger car diesel engine at steady conditions or under a certification cycle is made using in-house software. It is based on neural fitting of experimental data from eight different fuels tested under five operating steady conditions (reproducing modes of the European transient urban/extraurban certification cycle). The software allows the determination of PAH emissions as a function of the fuel composition parameters (aromatic content, cetane index, gross heat power, nitrogen and sulphur content) and operation conditions (torque and engine speed). The mathematical model reproduces experimental data with a maximum error of 20%. This tool is very useful, since changes in parameters can be made without experimental cost and the trend in modifications in PAH emissions is immediately obvious.

PAH effects on meio- and microbial benthic communities strongly depend on bioavailability.

PubMed

Lindgren, J Fredrik; Hassellöv, Ida-Maja; Dahllöf, Ingela

2014-01-01

The effects of anthropogenic pollutants in dissimilar habitats can vary depending on differences in bioavailability. The factors determining bioavailability are not yet fully understood. This study was performed to evaluate whether analysis of total PAH concentrations in sediments is a satisfactory measurement to indicate environmental effects or if bioavailability is needed to be taken into account. We have here performed a 60-day experiment, where nominal PAH concentrations of 1,300 μg/kg sediment were added to three different marine sediments. Meiofaunal and microbial communities were analyzed for alterations in community response at 30 and 60 days. Results showed that bioavailability of PAHs varied between the three different sediments. Nonetheless, the petroleum addition gave rise to significant negative effects on all three sediments at both time points. The two direct measurements of toxicity on the microbial community, potential nitrification and denitrification, displayed a lower effect of the PAH addition in the muddy sediment at both time points, compared to the other two sediment types. No effects were seen in the analysis of meiofaunal community structure. Measurements of PAH bioavailability in the three sediment types concurred with the results from the microbial community, revealing a lower bioavailability in the muddy sediment compared to the other two sediment types, 34% compared to sandy and 18% compared to organic at day 0. At day 60 it was 61% lower compared to sandy and 20% lower compared to organic. The negative effects of the PAH addition on the microbial nitrogen cycle were in six out of eight cases best correlated to the amount of alkylated bioavailable PAH in the sediments, and thus microbial nitrogen cycle is a possible good indicator for assessing PAH-induced stress. The results presented here have implications for risk analysis studies of petroleum-contaminated marine sediments; consequently, sediment characteristics and its effects on

The effect of sewage sludge fertilization on the concentration of PAHs in urban soils.

PubMed

Wołejko, Elżbieta; Wydro, Urszula; Jabłońska-Trypuć, Agata; Butarewicz, Andrzej; Łoboda, Tadeusz

2018-01-01

This paper analyses sources of sixteen PAHs - polycyclic aromatic hydrocarbons in urbanized areas by using selected diagnostic ratios. Simultaneously, an attempt was made to determine how sewage sludge changes PAHs content in urbanized areas soils. In the experiment three lawns along the main roads in Bialystok with different traffic intensity, three doses of sewage sludge and two years of study were considered. There was no effect of fertilization with sewage sludge on the sum of 16 PAHs in urban soil samples, nevertheless, the sum of 16 PAHs was reduced from 2.6 in 2011 to 2.3 mg/kg in 2012. Among 16 tested PAHs compounds, benzo[a]pyrene was the most dominant compound in samples collected in both years - about 15% of all PAHs. The results suggest that application of sludge into the soil did not influence the concentration of 2-3-ring, 4-ring and 5-6-ring PAHs. For the objects fertilized with a dose 150.0 Mg/ha, of sludge the total sum of potentially carcinogenic PAHs in the urban soil lowered by approximately 68% in comparison with the control plots. PAHs contamination of the urban soil samples resulted from the influence of coal, petroleum and biomass combustion. Moreover, PAHs can enter soil via at mospheric deposition. Copyright © 2017 Elsevier Ltd. All rights reserved.

Laboratory Spectra of CO2 Vibrational Modes in Planetary Ice Analogs

NASA Technical Reports Server (NTRS)

White, Douglas; Mastrapa, Rachel M.; Sandford, Scott

2012-01-01

Laboratory spectra have shown that CO2 is a powerful diagnostic tool for analyzing infrared data from remote observations, as it has been detected on icy moons in the outer Solar System as well as dust grain surfaces in the interstellar medium (ISM). IR absorption band profiles of CO2 within ice mixtures containing H2O and CH3OH change with respect to temperature and mixture ratios. In this particular study, the CO2 asymmetric stretching mode near 4.3 m (2350 cm (exp-1)), overtone mode near 1.97 m (5080 cm (exp-1)), and the combination bands near 2.7 m (3700 cm (exp-1)), 2.8 m (3600 cm (exp-1)), and 2.02 m (4960 cm (exp -1)), are systematically observed in different mixtures with H2O and CH3OH in temperature ranges from 15K to 150 K. Additionally, some high-temperature deposits (T greater than 50 K) of H2O, CH3OH, and CO2 ice mixtures were performed. These data may then be used to interpret infrared observational data obtained from icy surfaces in the outer Solar System and beyond.

Bioremediation of poly-aromatic hydrocarbon (PAH)-contaminated soil by composting

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

Loick, N.; Hobbs, P.J.; Hale, M.D.C.

2009-07-01

This paper presents a comprehensive and critical review of research on different co-composting approaches to bioremediate hydrocarbon contaminated soil, organisms that have been found to degrade PAHs, and PAH breakdown products. Advantages and limitations of using certain groups of organisms and recommended areas of further research effort are identified. Studies investigating the use of composting techniques to treat contaminated soil are broad ranging and differ in many respects, which makes comparison of the different approaches very difficult. Many studies have investigated the use of specific bio-additives in the form of bacteria or fungi with the aim of accelerating contaminant removal;more » however, few have employed microbial consortia containing organisms from both kingdoms despite knowledge suggesting synergistic relationships exist between them in contaminant removal. Recommendations suggest that further studies should attempt to systemize the investigations of composting approaches to bio-remediate PAH-contaminated soil, to focus on harnessing the biodegradative capacity of both bacteria and fungi to create a cooperative environment for PAH degradation, and to further investigate the array of PAHs that can be lost during the composting process by either leaching or volatilization.« less

Removing PAHs from urban runoff water by combining ozonation and carbon nano-onions.

PubMed

Sakulthaew, Chainarong; Comfort, Steve D; Chokejaroenrat, Chanat; Li, Xu; Harris, Clifford E

2015-12-01

Ozone (O3) is a chemical oxidant capable of transforming polycyclic aromatic hydrocarbons (PAHs) in urban runoff within minutes but complete oxidation to CO2 can take days to weeks. We developed and tested a flow-through system that used ozone to quickly transform PAHs in a runoff stream and then removed the ozone-transformed PAHs via adsorption to carbon nano-onions (CNOs). To quantify the efficacy of this approach, (14)C-labeled phenanthrene and benzo(a)pyrene, as well as a mixture of 16 unlabeled PAHs were used as test compounds. These PAHs were pumped from a reservoir into a flow-through reactor that continuously ozonated the solution. Outflow from the reactor then went to a chamber that contained CNOs to adsorb the ozone-transformed PAHs and allowed clean water to pass. By adding a microbial consortium to the CNOs following adsorption, we observed that bacteria were able to degrade the adsorbed products and release more soluble, biodegradable products back into solution. Control treatments confirmed that parent PAH structures (i.e., non-ozonated) were not biologically degraded following CNO adsorption and that O3-transformed PAHs were not released from the CNOs in the absence of bacteria. These results support the combined use of ozone, carbon nano-onions with subsequent biological degradation as a means of removing PAHs from urban runoff or a commercial waste stream. Copyright © 2015 Elsevier Ltd. All rights reserved.

Endocrine disrupting potential of PAHs and their alkylated analogues associated with oil spills.

PubMed

Lee, Sangwoo; Hong, Seongjin; Liu, Xiaoshan; Kim, Cheolmin; Jung, Dawoon; Yim, Un Hyuk; Shim, Won Joon; Khim, Jong Seong; Giesy, John P; Choi, Kyungho

2017-09-20

Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs are known to be major toxic contaminants in spills of petroleum hydrocarbons (oil). Spilled oil undergoes weathering and over time, PAHs go through a series of compositional changes. PAHs can disrupt endocrine functions, and the type of functions affected and associated potencies vary with the type and alkylation status of PAH. In this study, the potential of five major PAHs of crude oil, i.e., naphthalene, fluorene, dibenzothiophene, phenanthrene, and chrysene, and their alkylated analogues (n = 25), to disrupt endocrine functions was evaluated by use of MVLN-luc and H295R cell lines. In the MVLN-luc bioassay, seven estrogen receptor (ER) agonists were detected among 30 tested PAHs. The greatest ER-mediated potency was observed for 1-methylchrysene (101.4%), followed by phenanthrene and its alkylated analogues (range of %-E2max from 1.6% to 47.3%). In the H295R bioassay, significantly greater syntheses of steroid hormones were observed for 20 PAHs. For major PAHs and their alkylated analogues, disruption of steroidogenesis appeared to be more significant than ER-mediated effects. The number and locations of alkyl-moieties alone could not explain differences in the types or the potencies of toxicities. This observation shows that disruption of endocrine functions by some constituents of oil spills could be underestimated if only parent compounds are considered in assessments of hazard and risk.

Enhanced arsenic uptake and polycyclic aromatic hydrocarbon (PAH)-dissipation using Pteris vittata L. and a PAH-degrading bacterium.

PubMed

Sun, Lu; Zhu, Ganghui; Liao, Xiaoyong

2018-05-15

This study examined the effects of P. vittata and a polycyclic aromatic hydrocarbon (PAH)-degrading bacterium (Alcaligenes sp.) on arsenic (As) uptake and phenanthrene dissipation. Bacterial inoculation substantially increased As accumulation in plants by 27.8% (frond) and 27.5% (root) at 60d, respectively, compared with the non-inoculated treatment, although temporal change of As translocation and reduction in plants was observed. Bacterial inoculation positively affected plants by improving growth, nutrition and antioxidative activities, and helped to modify soil As availability to the plants, which may benefit in plant tolerance and As accumulation. Plant and bacteria association enhanced phenanthrene dissipation from the soil, with the highest dissipation rate of 96.4% at 60d in the rhizosphere, which might be associated with enhanced bacterial population and activity inspired by the growth of plant. The result reveals that combination of P. vittata and PAH-degrading bacteria can promote As accumulation and phenanthrene dissipation, and can be exploited as a promising strategy for As and PAH co-contamination remediation. Copyright © 2017 Elsevier B.V. All rights reserved.

Phytoremediation of polycyclic aromatic hydrocarbons (PAH) by cv. Crioula: A Brazilian alfalfa cultivar.

PubMed

Alves, Wilber S; Manoel, Evelin A; Santos, Noemi S; Nunes, Rosane O; Domiciano, Giselli C; Soares, Marcia R

2018-07-03

This work aimed to evaluate the phytoremediation capacity of the alfalfa cultivar Crioula in soils contaminated with polycyclic aromatic hydrocarbons (PAHs), primary pollutants with mutagenic and carcinogenic potential. Alfalfa was grown from seed for 40 days on soil amended with anthracene, pyrene, and phenanthrene. Soil and plant tissue was collected for biometric assay, dry mass analysis, and PAH analysis by liquid chromatography. Increased total PAH concentration was associated with decreases in plant biomass, height, and internode length. The Crioula cultivar had a satisfactory phytoremediation effect, reducing total PAH concentration (300 ppm) in the experimental soil by 85% in 20 days, and by more than 95% in 40 days. The PAH showed a tendency to be removed in the temporal order: phenanthrene before pyrene before anthracene, and the removal ratio was influenced by the initial soil concentration of each PAH.

Response of microbial activities and diversity to PAHs contamination at coal tar contaminated land

NASA Astrophysics Data System (ADS)

Zhao, Xiaohui; Sun, Yujiao; Ding, Aizhong; Zhang, Dan; Zhang, Dayi

2015-04-01

Coal tar is one of the most hazardous and concerned organic pollutants and the main hazards are polycyclic aromatic hydrocarbons (PAHs). The indigenous microorganisms in soils are capable to degrade PAHs, with essential roles in biochemical process for PAHs natural attenuation. This study investigated 48 soil samples (from 8 depths of 6 boreholes) in Beijing coking and chemistry plant (China) and revealed the correlation between PAHs contamination, soil enzyme activities and microbial community structure, by 16S rRNA denaturing gradient gel electrophoresis (DGGE). At the site, the key contaminants were identified as naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene and anthracene, and the total PAHs concentration ranged from 0.1 to 923.9 mg/kg dry soil. The total PAHs contamination level was positively correlated (p<0.05) with the bacteria count (0.9×107-14.2×107 CFU/mL), catalase activities (0.554-6.230 mL 0.02 M KMnO4/g•h) and dehydrogenase activities (1.9-30.4 TF μg/g•h soil), showing the significant response of microbial population and degrading functions to the organic contamination in soils. The PAHs contamination stimulated the PAHs degrading microbes and promoted their biochemical roles in situ. The positive relationship between bacteria count and dehydrogenase activities (p<0.05) suggested the dominancy of PAHs degrading bacteria in the microbial community. More interestingly, the microbial community deterioration was uncovered via the decline of microbial biodiversity (richness from 16S rRNA DGGE) against total PAHs concentration (p<0.05). Our research described the spatial profiles of PAHs contamination and soil microbial functions at the PAHs heavily contaminated sites, offering deeper understanding on the roles of indigenous microbial community in natural attenuation process.

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions.

PubMed

Zhou, Hui; Wu, Chunfei; Onwudili, Jude A; Meng, Aihong; Zhang, Yanguo; Williams, Paul T

2015-02-01

The formation of 2-4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock. Copyright © 2014 Elsevier Ltd. All rights reserved.

ASSESSING RISKS FROM PHOTOACTIVATED TOXICITY OF PAHS TO AQUATIC ORGANISMS

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) are one of the most ubiquitous classes of environmental contaminants. Although most PAHs are toxic only at concentrations large enough to cause narcosis, the toxicity of some can be greatly enhanced through mechanisms that involve molecul...

Energy sources of polycyclic aromatic hydrocarbons. [Carcinogenicity of PAHs

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

Guerin, M. R.

1977-01-01

Combustion is the predominant end-process by which fossil fuels are converted to energy. Combustion, particularly when inefficient, is also the primary technological source of polycyclic aromatic hydrocarbons (PAHs) released into the environment. The need for liquid fuels to supply the transportation industry and for nonpolluting fuels for heat and power generation provide the incentive to commercialize processes to convert coal to substitute natural gas and oil. These processes represent a potentially massive new source of environmental PAHs. Insuring an adequate supply of energy with minimum impact on the environment and on health is one of the most important, urgent, andmore » challenging goals currently facing science and technology. Polycyclic aromatic hydrocarbon related carcinogenesis is among the most important of possible occupational- and environmental-health impacts of much of the current and projected national energy base. An understanding of the relationship of polycyclic aromatic hydrocarbons (PAHs) to human cancer and a continued surveillance of energy sources for PAH content are necessary to minimize this impact.« less

Withdrawal of long-term epoprostenol therapy in pulmonary arterial hypertension (PAH).

PubMed

Calcaianu, George; Calcaianu, Mihaela; Canuet, Matthieu; Enache, Irina; Kessler, Romain

2017-01-01

Once initiated for pulmonary arterial hypertension (PAH), epoprostenol treatment usually needs to be delivered for an indefinite duration. It is possible that some participants could be transitioned from epoprostenol to oral therapies. We retrospectively evaluated eight PAH participants transitioned from epoprostenol to PAH oral drugs. The criteria for epoprostenol withdrawal were: (1) persistent improvement of clinic and hemodynamic status; (2) stable dose of epoprostenol for the last three months; and (3) the participant's preference for oral therapy after evaluation of risk-benefit. We evaluated the clinical, functional, and hemodynamic status at baseline, at withdrawal, and after the transition to oral PAH therapy. The transition was completed in all eight participants. Four participants had a complete successful transition (CT) with a stable clinical and hemodynamic course and four participants had a partial successful transition (PT) remaining stable clinically, with a mild hemodynamic worsening, but without need to re-initiate epoprostenol therapy. The four CT participants were treated with epoprostenol for a shorter period of time (CT group: 35 ± 30 versus PT group: 79 ± 49 months, P = 0.08). Mean epoprostenol dosage was lower in the CT group (CT group: 15 ± 1.5 ng/kg/min versus PT group: 24 ± 11 ng/kg/min, P = 0.09). Safe withdrawal of epoprostenol treatment and transition to oral PAH therapy was possible in a small and highly selected group of participants. The majority of these participants had a porto-pulmonary PAH or PAH associated to HIV infection.

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

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.

Priority PAHs in orthodox black tea during manufacturing process.

PubMed

Grover, Inderpreet Singh; Singh, Satnam; Pal, Bonamali

2013-08-01

Orthodox black tea is obtained from fresh leaves followed by withering, rolling, fermentation and drying. The presence of 16 priority polycyclic aromatic hydrocarbons (PAHs) was studied in fresh leaves and at various stages of manufacturing. Benzo(a)pyrene (2A: probable human carcinogen) was found in dried tea leaves only whereas, naphthalene (2B: probable human carcinogen) was present during all the stages of manufacturing. Dry tea leaves showed higher content of total 16 PAHs (∑PAHs) about 3 and 211 times than present in withered and dried leaves, respectively. Chrysene, benzo[g,h,i]perylene, indendo[1,2,3-c,d]pyrene, dibenzo[a,h]pyrene and benzo[a]antracene were not found during manufacturing stages of tea.

PHOTOINDUCED TOXICITY OF PAHS AND ALKYLATED PAHS TO A MARINE INFAUNAL AMPHIPOD (RHEPOXYNIUS ABRONIUS)

EPA Science Inventory

The marine infaunal amphipod Rhepoxynius abronius was exposed in standard 10-day toxicity tests to sediments contaminated with parent or alkylated PAHs. After exposures, mortalities (LC50 values) and the ability to rebury in control sediment (EC50 values) were determined. Survivo...

Excretion of polycyclic aromatic hydrocarbon metabolites (OH-PAHs) in cattle urine in Ghana.

PubMed

Bortey-Sam, Nesta; Ikenaka, Yoshinori; Akoto, Osei; Nakayama, Shouta M M; Marfo, Jemima; Saengtienchai, Aksorn; Mizukawa, Hazuki; Ishizuka, Mayumi

2016-11-01

Previous studies of polycyclic aromatic hydrocarbons (PAHs) in particulate matter, soils and livers of wild rats indicated that the city centre of Kumasi, Ghana has been severely polluted with high cancer potency. Cattle urine were therefore collected from Kumasi (urban) and Offinso (rural), Ghana: to determine concentrations of urinary PAH metabolites (OH-PAHs); and find their association with sex; and to estimate exposure of cattle to PAHs from the different sites. From the results, geometric mean concentrations (adjusted by specific gravity), GM SG , showed that 2-OHNaphthalene (2-OHNap) was the most abundant OH-PAH in cattle urine from all study sites, and naphthalene-containing-mothballs might have contributed significantly to the levels. There was no significant difference between urinary OH-PAHs concentrations in cattle from urban and rural sites except for 2-OHPhe and 4-OHPhe, and similar to urban areas, rural sites could also be polluted with PAHs. GM SG of 2-OHNap in cattle urine in Kokote (21.9 ± 6.51 ng/mL; a rural area), was significantly higher compared to the other sites followed by Oforikrom (4.15 ± 4.37 ng/mL; urban). The GM SG concentration (ng/mL) of the sum of OH-PAHs decreased in the order, Kokote (44.7) > Oforikrom (7.87) > Saboa (6.98) > Santasi (6.68) > and Twumasen Estate (5.23). The high concentrations of urinary 2-OHNap, 2-3-OHFlu, 2-OHPhe, 3-OHPhe and 4-OHPhe in Kokote indicated high PAHs exposure to cattle in this area or different/specific source of PAHs exposure. GM SG of 2-OHNap was significantly higher in male cattle compared to females while 1-9-OHPhe was significantly higher in females. Copyright © 2016. Published by Elsevier Ltd.

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

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

Raj, Abhijeet; Celnik, Matthew; Shirley, Raphael

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

Are Urinary PAHs Biomarkers of Controlled Exposure to Diesel Exhaust?

EPA Science Inventory

Urinary polycyclic aromatic hydrocarbons (PAHs) were evaluated as possible biomarkers of exposure to diesel exhaust (DE) in two controlled-chamber studies. We report levels of 14 PAHs from 28 subjects in urine that were collected before, immediately after and the morning after ex...

Manipulating Ratio Spectra for the Spectrophotometric Analysis of Diclofenac Sodium and Pantoprazole Sodium in Laboratory Mixtures and Tablet Formulation

PubMed Central

Bhatt, Nejal M.; Chavada, Vijay D.; Sanyal, Mallika; Shrivastav, Pranav S.

2014-01-01

Objective. Three sensitive, selective, and precise spectrophotometric methods based on manipulation of ratio spectra, have been developed and validated for the determination of diclofenac sodium and pantoprazole sodium. Materials and Methods. The first method is based on ratio spectra peak to peak measurement using the amplitudes at 251 and 318 nm; the second method involves the first derivative of the ratio spectra (Δλ = 4 nm) using the peak amplitudes at 326.0 nm for diclofenac sodium and 337.0 nm for pantoprazole sodium. The third is the method of mean centering of ratio spectra using the values at 318.0 nm for both the analytes. Results. All the three methods were linear over the concentration range of 2.0–24.0 μg/mL for diclofenac sodium and 2.0–20.0 μg/mL for pantoprazole sodium. The methods were validated according to the ICH guidelines and accuracy, precision, repeatability, and robustness are found to be within the acceptable limit. The results of single factor ANOVA analysis indicated that there is no significant difference among the developed methods. Conclusions. The developed methods provided simple resolution of this binary combination from laboratory mixtures and pharmaceutical preparations and can be conveniently adopted for routine quality control analysis. PMID:24701171

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.

Indoor PAHs at schools, homes and offices in Rome, Italy

NASA Astrophysics Data System (ADS)

Romagnoli, P.; Balducci, C.; Perilli, M.; Gherardi, M.; Gordiani, A.; Gariazzo, C.; Gatto, M. P.; Cecinato, A.

2014-08-01

Indoor and outdoor concentrations of polycyclic aromatic hydrocarbons (PAHs) associated with PM2.5 particles were monitored in three microenvironments (schools, homes and offices) in the city of Rome, Italy, between winter 2011 and summer 2012. Molecular signatures and indoor/outdoor concentration ratios of PAHs were investigated, with special emphasis on carcinogenic congeners. At indoor locations, total PAHs ranged, on average, from 1.8 to 8.4 ng/m3 in winter and from 0.30 to 1.35 ng/m3 in spring/summer. Outdoors, total PAH concentrations were found to reach 6.3-17.9 ng/m3 in winter and 0.42-1.74 ng/m3 in spring-summer. Indoors, the concentration of benzo[a]pyrene (BaP) was as high as 1.1 ng/m3 in winter and below 0.1 ng/m3 in the warm season, independently of site type; the yearly average remained below the European guideline value. The indoor/outdoor concentration ratios of individual compounds were lower than one for most of congeners, suggesting that outdoor sources were predominant. Nonetheless, the percentages of PAH compounds changed with sites and seasons; in particular, in spring/summer, the concentration of BaP at our sites was more than twice that recorded at the regional network stations.

Formation of nitro-PAHs from the heterogeneous reaction of ambient particle-bound PAHs with N2O5/NO3/NO2

PubMed Central

Zimmermann, Kathryn; Jariyasopit, Narumol; Massey Simonich, Staci L.; Tao, Shu; Atkinson, Roger; Arey, Janet

2014-01-01

Reactions of ambient particles collected from four sites within the Los Angeles, CA air basin and Beijing, China with a mixture of N2O5, NO2, and NO3 radicals were studied in an environmental chamber at ambient pressure and temperature. Exposures in the chamber system resulted in the degradation of particle-bound PAHs and formation of molecular weight (mw) 247 nitropyrenes (NPYs) and nitrofluoranthenes (NFLs), mw 273 nitrotriphenylenes (NTPs), nitrobenz[a]anthracenes (NBaAs), and nitrochrysene (NCHR), and mw 297 nitrobenzo[a]pyrene (NBaP). The distinct isomer distributions resulting from exposure of filter-adsorbed deuterated fluoranthene to N2O5/NO3/NO2 and that collected from the chamber gas-phase suggest that formation of NFLs in ambient particles did not occur by NO3 radical-initiated reaction, but from reaction of N2O5, presumably subsequent to its surface adsorption. Accordingly, isomers known to result from gas-phase radical-initiated reactions of parent PAHs, such as 2-NFL and 2- and 4-NPY, were not enhanced from the exposure of ambient particulate matter to N2O5/NO3/NO2. The reactivity of ambient particles toward nitration by N2O5/NO3/NO2, defined by relative 1-NPY formation, varied significantly, with the relative amounts of freshly emitted particles versus aged particles (particles that had undergone atmospheric chemical processing) affecting the reactivity of particle-bound PAHs toward heterogeneous nitration. Analyses of unexposed ambient samples suggested that, in nighttime samples where NO3 radical-initiated chemistry had occurred, heterogeneous formation of 1-NPY on ambient particles may have contributed to the ambient 1-NPY concentrations at downwind receptor sites. These results, together with observations that 2-NFL is consistently the dominant particle-bound nitro-PAH measured in ambient atmospheres, suggest that for PAHs that exist in both the gas- and particle-phase, the heterogeneous formation of particle-bound nitro-PAHs is a minor formation

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

USGS Publications Warehouse

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

2010-01-01

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

Determination of oxygen, nitrogen, and sulfur-containing polycyclic aromatic hydrocarbons (PAHs) in urban stream sediments.

PubMed

Witter, Amy E; Nguyen, Minh H

2016-02-01

Recent studies indicate that PAH transformation products such as ketone or quinone-substituted PAHs (OPAHs) are potent aryl hydrocarbon receptor (AhR) activators that elicit toxicological effects independent of those observed for PAHs. Here, we measured eight OPAHs, two sulfur-containing (SPAH), one oxygen-containing (DBF), and one nitrogen-containing (CARB) heterocyclic PAHs (i.e. ΣONS-PAHs = OPAH8 + SPAH + DBF + CARB) in 35 stream sediments collected from a small (∼1303 km(2)) urban watershed located in south-central Pennsylvania, USA. Combined ΣONS-PAH concentrations ranged from 59 to 1897 μg kg(-1) (mean = 568 μg kg(-1); median = 425 μg kg(-1)) and were 2.4 times higher in urban versus rural areas, suggesting that activities taking place on urban land serve as a source of ΣONS-PAHs to sediments. To evaluate urban land use metrics that might explain these data, Spearman rank correlation analyses was used to evaluate the degree of association between ΣONS-PAH concentrations and urban land-use/land-cover metrics along an urban-rural transect at two spatial scales (500-m and 1000-m upstream). Combined ΣONS-PAH concentrations showed highly significant (p < 0.0001) correlations with ΣPAH19, residential and commercial/industrial land use (RESCI), and combined state and local road miles (MILES), suggesting that ΣONS-PAHs originate from similar sources as PAHs. To evaluate OPAH sources, a subset of ΣONS-PAHs for which reference assemblages exist, an average OPAH fractional assemblage for urban sediments was derived using agglomerative hierarchal cluster (AHC) analysis, and compared to published OPAH source profiles. Urban sediments from the Condoguinet Creek (n = 21) showed highly significant correlations with urban particulate matter (X(2) = 0.05, r = 0.91, p = 0.0047), suggesting that urban particulate matter is an important OPAH source to sediments in this watershed. Results suggest the inclusion of ΣONS-PAH measurements

Influence of heavy metals on the formation and the distribution behavior of PAH and PCDD/F during simulated fires.

PubMed

Wobst, M; Wichmann, H; Bahadir, M

2003-04-01

Combustion experiments were performed with an artificial fire load (polystyrene and quartz powder) in a laboratory scale incinerator in the presence of gaseous HCl to simulate accidental fire conditions. The aim of this investigation was to trace back the alterations of the formation and the distribution behavior of PAH and PCDD/PCDF to the presence of CuO or a mixture of metal oxides (CdO, CuO, Fe(2)O(3), PbO, MoO(3), ZnO). The total amount of the 16 PAH target compounds was reduced by the factor of 5-9 when the mixture of metal oxides was present rather than merely CuO. PAH patterns as well as their distribution behavior were significantly influenced by these oxides. In general, transportation inside the installation was enhanced for most of the 16 analyzed PAH. Only fluorene and dibenzo[a,h]anthracene were transported to a smaller extent. In contrast to PAH, total concentrations of PCDD were increased by factor 9 and of PCDF by factor 10, respectively, when CuO was present. Adding the mixture of metal oxides resulted in an increase of PCDD by factor 14 and of PCDF by factor 7. CuO and the mixture of metal oxides had a different influence on the PCDD/F homologue patterns. For instance, the HxCDF to OCDF ratio after incineration without any metal oxide was 1 to 6, whereas addition of CuO or the mixture of the metal oxides shifted the HxCDF to OCDF ratios towards 1 to 40 or 1 to 17, respectively. Combustion along with CuO increased transportation of higher chlorinated PCDF congeners, whereas the mixture of the metal oxides caused a strong decrease of PCDF distribution throughout the system.