Complex Polycyclic Aromatic Hydrocarbons Research Articles

Polycyclic aromatic hydrocarbon: underpinning the contribution of specialist microbial species to contaminant mitigation in the soil.

The persistence of PAHs poses a significant challenge for conventional remediation approaches, necessitating the exploration of alternative, sustainable strategies for their mitigation. This review underscores the vital role of specialized microbial species (nitrogen-fixing, phosphate-solubilizing, and biosurfactant-producing bacteria) in tackling the environmental impact of polycyclic aromatic hydrocarbons (PAHs). These resistant compounds demand innovative remediation strategies. The study explores microbial metabolic capabilities for converting complex PAHs into less harmful byproducts, ensuring sustainable mitigation. Synthesizing literature from 2016 to 2023, it covers PAH characteristics, sources, and associated risks. Degradation mechanisms by bacteria and fungi, key species, and enzymatic processes are examined. Nitrogen-fixing and phosphate-solubilizing bacteria contributions in symbiotic relationships with plants are highlighted. Biosurfactant-producing bacteria enhance PAH solubility, expanding microbial accessibility for degradation. Cutting-edge trends in omics technologies, synthetic biology, genetic engineering, and nano-remediation offer promising avenues. Recommendations emphasize genetic regulation, field-scale studies, sustainability assessments, interdisciplinary collaboration, and knowledge dissemination. These insights pave the way for innovative, sustainable PAH-contaminated environment restoration.

Observation of bound valence excited electronic states of deprotonated 2-hydroxytriphenylene using photoelectron, photodetachment, and resonant two-photon detachment spectroscopy of cryogenically cooled anions.

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh-), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh- anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh- anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh-, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh- would be an interesting system for pump-probe experiments to unravel the dynamics of the excited states of this complex PAH anion.

Large-scale atomistic model construction of subbituminous and bituminous coals for solvent extraction simulations with reactive molecular dynamics

Large-scale atomistic models for complex polycyclic aromatic hydrocarbon systems help understand the chemical properties and behaviors of complex feedstocks such as coal or petroleum. However, the development and utilization of large-scale models remain limited due to the difficulty in achieving the varied structural characteristics necessary to capture stochastic nature of these feedstocks. We demonstrate a systematic workflow to construct stochastic molecular systems from a broad analytical suite: high-resolution transmission electron microscopy (HRTEM), carbon-13 nuclear magnetic resonance spectroscopy (13C NMR), laser desorption ionization mass spectroscopy (LDI-MS), and elemental analysis. We present a model construction and analysis utility of a new Python-based module. We selected one subbituminous and three high-volatile bituminous coals to construct large-scale models (∼40,000 atoms). The constructed models were utilized to examine the affinity for solvent extraction (naphthalene or tetralin) and the effect of structural properties (e.g., aromatic cluster size, functional groups, and cross-linking) in reactive molecular dynamics simulations. Complex chemical reactions were monitored with bond order transitions, intermediates formation, and mass distributions. Reactive molecular dynamics simulations suggest a plausible chemical extraction process and products for the complex fossil feedstocks. The results indicated that radical formations with bond breaking of bridging oxygens and carbons were required at high temperatures to facilitate hydrogeneration and extraction of gas molecules from radical-free molecules. We observed that aliphatic chains of tetralin were easily decomposed and combined with radicals to form small size of molecules with aryl bonding, mainly increasing molecules in the 500–1000 Da, while naphthalene had little impact on chemical extraction process.

Unconventional gas-phase synthesis of biphenyl and its atropisomeric methyl-substituted derivatives.

The biphenyl molecule (C12H10) acts as a fundamental molecular backbone in the stereoselective synthesis of organic materials due to its inherent twist angle causing atropisomerism in substituted derivatives and in molecular mass growth processes in circumstellar environments and combustion systems. Here, we reveal an unconventional low-temperature phenylethynyl addition-cyclization-aromatization mechanism for the gas-phase preparation of biphenyl (C12H10) along with ortho-, meta-, and para-substituted methylbiphenyl (C13H12) derivatives through crossed molecular beams and computational studies providing compelling evidence on their formation via bimolecular gas-phase reactions of phenylethynyl radicals (C6H5CC, X2A1) with 1,3-butadiene-d6 (C4D6), isoprene (CH2C(CH3)CHCH2), and 1,3-pentadiene (CH2CHCHCHCH3). The dynamics involve de-facto barrierless phenylethynyl radical additions via submerged barriers followed by facile cyclization and hydrogen shift prior to hydrogen atom emission and aromatization to racemic mixtures (ortho, meta) of biphenyls in overall exoergic reactions. These findings not only challenge our current perception of biphenyls as high temperature markers in combustion systems and astrophysical environments, but also identify biphenyls as fundamental building blocks of complex polycyclic aromatic hydrocarbons (PAHs) such as coronene (C24H12) eventually leading to carbonaceous nanoparticles (soot, grains) in combustion systems and in deep space thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.

The Galaxy Activity, Torus, and Outflow Survey (GATOS)

We use JWST/MIRI MRS spectroscopy of a sample of six local obscured type 1.9/2 active galactic nuclei (AGN) to compare their nuclear mid-IR absorption bands with the level of nuclear obscuration traced by X-rays. This study is the first to use subarcsecond angular resolution data of local obscured AGN to investigate the nuclear mid-IR absorption bands with a wide wavelength coverage (4.9–28.1 μm). All the nuclei show the 9.7 μm silicate band in absorption. We compare the strength of the 9.7 and 18 μm silicate features with torus model predictions. The observed silicate features are generally well explained by clumpy and smooth torus models. We report the detection of the 6 μm dirty water ice band (i.e., a mix of water and other molecules such as CO and CO2) at subarcsecond scales (∼0.26″ at 6 μm; inner ∼50 pc) in a sample of local AGN with different levels of nuclear obscuration in the range log NHX-Ray (cm−2)∼22 − 25. We find good correlation between the 6 μm water ice optical depths and NHX-Ray. This result indicates that the water ice absorption might be a reliable tracer of the nuclear intrinsic obscuration in AGN. The weak water ice absorption in less obscured AGN (log NHX-ray (cm−2)≲23.0 cm−2) might be related to the hotter dust temperature (> TsubH2O ∼ 110 K) expected to be reached in the outer layers of the torus due to their more inhomogeneous medium. Our results suggest it might be necessary to include the molecular content, such as H2O, aliphatic hydrocarbons (CH−), and more complex polycyclic aromatic hydrocarbon (PAH) molecules, in torus models to better constrain key parameters such as the torus covering factor (i.e., nuclear obscuration).

Degradation of the highly complex polycyclic aromatic hydrocarbon coronene by the halophilic bacterial strain Halomonas caseinilytica, 10SCRN4D

Degradation of the highly complex polycyclic aromatic hydrocarbon coronene by the halophilic bacterial strain Halomonas caseinilytica, 10SCRN4D

Anharmonic IR absorption spectra of the prototypical interstellar PAHs phenanthrene, pyrene, and pentacene in their neutral and cation states

Combination band and overtone transitions of polycyclic aromatic hydrocarbon (PAH) cations in the 2000–2900 cm-1 (5-3.5 µm) region are implicated as carriers of the ‘quasi-continuum’ observed in the near-infrared (IR) emission spectra of many astronomical objects. In neutral PAHs, the strongest absorption features are concentrated in the 700–900 cm-1 (14–11 µm) range, which are associated with CH out-of-plane bending motions. Upon ionization, this shifts to the 1000–1600 cm-1 (10–6 µm) range, where bands are associated with C=C stretches and CH in-plane bends. Anharmonicity is required to accurately characterize the IR absorption spectrum of PAHs, indicated herein by the ability to directly assign the bands in high-resolution experimental absorption spectra of neutral and cationic phenanthrene, pyrene, and pentacene. Neutral PAHs are indicated as the source of the strong 3.3 and 11.2 µm astronomical PAH features, while the broad features in the 6–10 µm region and the ‘quasi-continuum’ from 3.5–5 µm stem from PAH cations. This study reinforces the need for including anharmonicity in the computation of IR absorption and emission spectra of larger and more complex PAHs. This is particularly pertinent to the interpretation of data returned by JWST.

Gas-phase formation of the resonantly stabilized 1-indenyl (C9H7•) radical in the interstellar medium.

The 1-indenyl (C9H7•) radical, a prototype aromatic and resonantly stabilized free radical carrying a six- and a five-membered ring, has emerged as a fundamental molecular building block of nonplanar polycyclic aromatic hydrocarbons (PAHs) and carbonaceous nanostructures in deep space and combustion systems. However, the underlying formation mechanisms have remained elusive. Here, we reveal an unconventional low-temperature gas-phase formation of 1-indenyl via barrierless ring annulation involving reactions of atomic carbon [C(3P)] with styrene (C6H5C2H3) and propargyl (C3H3•) with phenyl (C6H5•). Macroscopic environments like molecular clouds act as natural low-temperature laboratories, where rapid molecular mass growth to 1-indenyl and subsequently complex PAHs involving vinyl side-chained aromatics and aryl radicals can occur. These reactions may account for the formation of PAHs and their derivatives in the interstellar medium and carbonaceous chondrites and could close the gap of timescales of their production and destruction in our carbonaceous universe.

Paving the way to the synthesis of PAHs in dark molecular clouds: The formation of cyclopentadienyl radical (c-C5H5)

Context. The interest of astrophysicists and astrochemists in studying polycyclic aromatic hydrocarbons (PAHs) has grown since their assignment to previously unidentified IR emission bands of dust grains. Although observations show that PAHs are present in the interstellar medium (ISM), there is still no consensus about their formation. PAH formation has been studied following two approaches: bottom-up (i.e. through the association of smaller hydrocarbons) and top-down (via the photo-dissociation or hydrogenation of larger-structures). The recent detection of simple aromatic rings in the TMC-1 molecular cloud seems to suggest the bottom-up scenario is favoured. Aims. We study the reaction between the propargyl (C3H3) radical and the vinyl radical (C2H3) under interstellar conditions, providing new kinetic parameters for the formation of PAH precursors. Methods. We used high-level quantum-chemical calculations to describe the reaction mechanism between these two radicals. We calculated the rate constant of the individual product channels in the temperature range 10–400 K and at 1 × 10−7 atm by solving the one-dimensional master equation to quantitatively understand whether this reaction is viable in the ISM. Results. Our results show that this reaction is likely to occur even in the low-density (~104 cm−3) and low-temperature (~10 K) conditions of molecular dark clouds. The main product is the cyclopentadienyl radical (C5H5). The unsaturated open-chain hydrocarbon C5H5 in the trans (trans-C5H5) and cis conformations (cis-C5H5) are also formed, but to a lesser extent. Conclusions. Our results show that the reaction of vinyl radical with propargyl radical is efficient under interstellar conditions and yields the cyclopentadienyl radical, which could be an important precursor for the formation of more complex polycyclic hydrocarbons (e.g. indene) and simple PAHs (e.g. naphthalene) in molecular dark clouds.

Decomposition mechanisms of nuclear-grade cationic exchange resin by advanced oxidation processes: Statistical molecular fragmentation model and DFT calculations

The treatment and disposal of radioactive waste are presently facing great challenges. Spent ion exchange resins have become a focus of attention due to their high production and serious environmental risks. In this paper, a simplified model of cationic exchange resin is proposed, and the degradation processes of cationic resin monomer initiated by hydroxyl radicals (·OH) are clarified by combining statistical molecular fragmentation (SMF) model and density functional theory (DFT) calculations. The prediction of active sites indicates that the S-O bonds and the C-S bond of the sulfonic group are more likely to react during the degradation. The meta-position of the sulfonic group on the benzene ring is the most active site, and the benzene ring without the sulfonic group has a certain reactivity. The C11-C14 and C17-C20 bonds, on the carbon skeleton, are the most easily broken. It is also found that dihydroxy addition and elimination reactions play a major role in the process of desulfonation, carbon skeleton cleavage and benzene ring separation. The decomposition mechanisms found through the combination of physical models and chemical calculations, provide theoretical guidance for the treatment of complex polycyclic aromatic hydrocarbons.

Mixed polyaromatic hydrocarbon degradation by halotolerant bacterial strains from marine environment and its metabolic pathway

Accidents involving diesel oil spills are prevalent in sea- and coastal regions. Polycyclic aromatic hydrocarbons (PAHs) can be adsorbed in soil and constitute a persistent contaminant due to their poor water solubility and complex breakdown. PAHs pollution is a pervasive environmental concern that poses serious risks to human life and ecosystems. Thus, it is the need of the hour to degrade and decontaminate the toxic pollutant to save the environment. Among all the available techniques, microbial degradation of the PAHs is proving to be greatly beneficial and effective. Bioremediation overcomes the drawbacks of most physicochemical procedures by eliminating numerous organic pollutants at a lower cost in ambient circumstances and has therefore become a prominent remedial option for pollutant removal, including PAHs. In the present study, we have studied the degradation of Low molecular Weight and High Molecular Weight PAH in combination by bacterial strains isolated from a marine environment. Optimum pH, temperature, carbon, and nitrogen sources, NaCl concentrations were found for efficient degradation using the isolated bacterial strains. At 250 mg/L concentration of the PAH mixture an 89.5% degradation was observed. Vibrio algiolytcus strains were found to be potent halotolerant bacteria to degrade complex PAH into less toxic simple molecules. GC-MS and FTIR data were used to probe the pathway of degradation of PAH.

Particle size-resolved emission characteristics of complex polycyclic aromatic hydrocarbon (PAH) mixtures from various combustion sources

Combustion of domestic solid fuels is a significant source of polycyclic aromatic hydrocarbons (PAHs). Some oxygenated PAHs (o-PAHs) and PAHs with molecular weight of 302 (MW302 PAHs) are more toxic than the traditional 16 priority PAHs, whereas their emissions were much less elucidated. This study characterized the size-dependent emissions of parent PAHs (p-PAHs), o-PAHs, and MW302 PAHs from various combustion sources. The estimated emission factors (eEFs) from biomass burning sources were highest for most of the PAHs (391–8928 μg/kg), much higher than that of anthracite coal combustion (43.0–145 μg/kg), both which were operated in an indoor stove. Cigarette smoking had a high eEF of o-PAHs (240 ng/g). MW302 PAHs were not found in the emissions of smoking, cooking, and vehicular exhausts. Particle-size distributions of PAHs were compound- and source-dependent, and the tendency to associate with smaller particles was observed especially in biomass burning and cigarette smoking sources. Furthermore, the inter-source differences in PAH eEFs were associated with their dominance in fine particles. PAH composition profiles also varied with the particle size, showing increasing contributions of large-molecule PAHs with decreasing sizes in most cases. The size distributions of p-PAHs are much more significantly dependent on their n-octanol/air partition coefficients and vapor pressures than those of o-PAHs, suggesting differences in mechanisms governing their distributions. Several molecular diagnostic ratios (MDRs), including two based on MW302 PAHs, specific to these combustion scenarios were identified. However, the MDRs within some sources are also strongly size-dependent, providing a new explanation for the uncertainty in their application for source identification of PAHs. This work also highlights the necessity for understanding the size-resolved atmospheric behaviors and fate of PAHs after their emission.

Pennisetum purpureum Improved Polycyclic Aromatic Hydrocarbons Removal in Weathered-Petroleum Contaminated Soil

Petroleum hydrocarbons are among the major driving forces of advancement in the last Century. Some of the hydrocarbons especially polycyclic aromatics are however of health and environmental significance, due to their recalcitrance and persistence leading to adverse effects on health and ecosystem stability. A number of treatment technologies have been used to cleanup hydrocarbon contaminants and the use of phytoremediation technology have recently been described as promising. In this study, phytoremediation of weathered crude oil contaminated soil was carried out in a microcosm using Pennisetumpurpureum for 60 days. Pristine soil samples were collected and mixed with weathered petroleum contaminated soil to achieve 5%, 25%, 35% and 50% w/w contamination levels. Bacterial species in the rhizosphere were isolated and identified and residual oil was extracted and analyzed using GC-MS. Results showed that there was high bacterial population in rhizosphere (5.0×105 cfu/g to 6.4×105 cfu/g) than non-rhizosphere soil (2.4 ×105 cfu/g to 4.0×105 cfu/g); and Bacillus spp. (64.71%) were observed to be predominant in the rhizosphere followed by Micrococcus spp. (17.65%), Pseudomonas aeruginosa (5.88%), Klebsiella pneumoniae (5.88%) and Flavobacterium sp. (5.88%). Hydrocarbon concentration in the rhizosphere was reduced by 82.5%, 60.5%, 58.0% and 48.8% respectively. Complex polycyclic aromatic hydrocarbon compounds detected in the control using GC-MS were significantly reduced or completely degraded. Polycyclic aromatic hydrocarbons such as anthracene, naphthalene, fluorene, benzo (a) anthracene, pyrene and chrysene were significantly reduced at a rate ranging between 13.33% and 97.54%. Based on the rate of PAHs reduction observed in this study, it was evident that P. purpureumsupports cleanup of persistent hydrocarbon contaminants in soil environment. The use of this plant in large scale petroleum hydrocarbon cleanup under field conditions should be investigated.

Formation of astrochemically relevant molecular ions: Reaction of translationally coldCCl+with benzene in a linear ion trap

The gas-phase ion-neutral reaction of ${\mathrm{CCl}}^{+}$ $+$ benzene $({\mathrm{C}}_{6}{\mathrm{H}}_{6})$ is investigated using a linear Paul ion trap coupled to a time-of-flight mass spectrometer. Low collision energies are achieved by sympathetically cooling ${\mathrm{CCl}}^{+}$ reactant ions with cotrapped laser-cooled ${\mathrm{Ca}}^{+}$. The observed products include the astrochemically relevant carbocations ${\mathrm{C}}_{7}{\mathrm{H}}_{5}^{+}$, ${\mathrm{C}}_{5}{\mathrm{H}}_{3}^{+}$, and ${\mathrm{C}}_{3}{\mathrm{H}}_{3}^{+}$, as well as ${\mathrm{C}}_{3}{\mathrm{H}}_{2}{\mathrm{Cl}}^{+}$. Branching ratios of these products are measured, and ${\mathrm{C}}_{7}{\mathrm{H}}_{5}^{+}$, a carbon-growth species, is favored. Complementary electronic structure calculations provide thermodynamic limits for the reaction and allow for assignment of reaction products to specific structural isomers. Only one exoergic isomer is identified for each observed product with the exception of ${\mathrm{C}}_{7}{\mathrm{H}}_{5}^{+}$ where many identified structural isomers are exoergic. The results from this Letter broaden our understanding of the reactivity and possible role of ${\mathrm{CCl}}^{+}$ and ${\mathrm{C}}_{6}{\mathrm{H}}_{6}$ in interstellar chemistry. Furthermore, this Letter provides insight into a potential pathway to larger carbocations that may be precursors to more complex polycyclic aromatic hydrocarbons.

Automated High-Resolution Semi-Preparative Gradient Recycling Liquid Chromatography: Principles, Design, and Applications

A semi-preparative twin-column recycling liquid chromatography (TCRLC) process was extended from isocratic to gradient elution mode. The main separation challenge is when the sample mixture contains early, nearly coeluting, and late impurities, all at the same time. To further improve classical isocratic TCRLC, the gradient TCRLC (GTCRLC) process was implemented with a 2-position 4-port valve in order to better shave the targeted sample from all these impurities. Prior to fully resolving the target compound(s) from the closest impurities by classical isocratic TCRLC, the added valve enabled full elimination by gradient elution mode of not only the early impurities but also any highly retained late impurities that could contaminate the collected fractions of the target compound(s). This GTCRLC process was entirely automated regarding the initial gradient applied, the recycling conditions, and the actuation times of the two valves. The GTCRLC process was applied for the isolation of a single polycyclic aromatic hydrocarbon (PAH), chrysene, present in a complex PAH mixture. In addition, the GTCRLC process was successfully applied to clean vitamins D2 and D3 from a milk extract and to baseline resolve them.

Application of Text Mining in Risk Assessment of Chemical Mixtures: A Case Study of Polycyclic Aromatic Hydrocarbons (PAHs).

Background:Cancer risk assessment of complex exposures, such as exposure to mixtures of polycyclic aromatic hydrocarbons (PAHs), is challenging due to the diverse biological activities of these compounds. With the help of text mining (TM), we have developed TM tools—the latest iteration of the Cancer Risk Assessment using Biomedical literature tool (CRAB3) and a Cancer Hallmarks Analytics Tool (CHAT)—that could be useful for automatic literature analyses in cancer risk assessment and research. Although CRAB3 analyses are based on carcinogenic modes of action (MOAs) and cover almost all the key characteristics of carcinogens, CHAT evaluates literature according to the hallmarks of cancer referring to the alterations in cellular behavior that characterize the cancer cell.Objectives:The objective was to evaluate the usefulness of these tools to support cancer risk assessment by performing a case study of 22 European Union and U.S. Environmental Protection Agency priority PAHs and diesel exhaust and a case study of PAH interactions with silica.Methods:We analyzed PubMed literature, comprising 57,498 references concerning priority PAHs and complex PAH mixtures, using CRAB3 and CHAT.Results:CRAB3 analyses correctly identified similarities and differences in genotoxic and nongenotoxic MOAs of the 22 priority PAHs and grouped them according to their known carcinogenic potential. CHAT had the same capacity and complemented the CRAB output when comparing, for example, benzo[a]pyrene and dibenzo[a,l]pyrene. Both CRAB3 and CHAT analyses highlighted potentially interacting mechanisms within and across complex PAH mixtures and mechanisms of possible importance for interactions with silica.Conclusion:These data suggest that our TM approach can be useful in the hazard identification of PAHs and mixtures including PAHs. The tools can assist in grouping chemicals and identifying similarities and differences in carcinogenic MOAs and their interactions. https://doi.org/10.1289/EHP6702

A comprehensive investigation on the chemical structure character of spinnable pitch for improving and optimizing the oxidative stabilization of coal tar pitch-based fiber

Oxidative stabilization is the critical step to maintain the fibrous morphology of pitch fiber and affects mechanical properties of resultant carbon fiber, but the detailed oxidation mechanism is still unclear because of the complex polycyclic aromatic hydrocarbons composition in pitch fiber. In here, pitch fiber was obtained from coal tar pitch followed by air-blowing and spinning. The chemical structure character of corresponding fibers before and after oxidative stabilization at different temperatures (260–320 °C) and durations (2–12 h) were analyzed. The results indicated that aromatic nucleus in spinnable pitch was gradually increased, while aliphatic chains were gradually shorten with prolongation of air-blowing time. The spinnable pitch obtained by air-blowing at 330 °C for 4 h showed excellent spinning performance, and the as-spun pitch fiber displayed a higher oxidative stabilization efficiency because the lower oxygen content was introduced and more C-O-C groups were formed in the resultant oxidative stabilized pitch fiber. The obtained pitch-based carbon fiber, after carbonizing at 1000 °C, showed excellent mechanical properties with tensile strength of 1068.7 ± 100.0 MPa and Young's modulus of 52.5 ± 9.8 GPa. This work provided a facile approach to improve and optimize the oxidative stabilization efficiency for pitch carbon fiber preparation.

Reactivity Trends in the Gas-Phase Addition of Acetylene to the N-Protonated Aryl Radical Cations of Pyridine, Aniline, and Benzonitrile.

A key step in gas-phase polycyclic aromatic hydrocarbon (PAH) formation involves the addition of acetylene (or other alkyne) to σ-type aromatic radicals, with successive additions yielding more complex PAHs. A similar process can happen for N-containing aromatics. In cold diffuse environments, such as the interstellar medium, rates of radical addition may be enhanced when the σ-type radical is charged. This paper investigates the gas-phase ion-molecule reactions of acetylene with nine aromatic distonic σ-type radical cations derived from pyridinium (Pyr), anilinium (Anl), and benzonitrilium (Bzn) ions. Three isomers are studied in each case (radical sites at the ortho, meta, and para positions). Using a room temperature ion trap, second-order rate coefficients, product branching ratios, and reaction efficiencies are measured. The rate coefficients increase from para to ortho positions. The second-order rate coefficients can be sorted into three groups: low, between 1 and 3 × 10-12 cm3 molecule-1 s-1 (3Anl and 4Anl); intermediate, between 5 and 15 × 10-12 cm3 molecule-1 s-1 (2Bzn, 3Bzn, and 4Bzn); and high, between 8 and 31 × 10-11 cm3 molecule-1 s-1 (2Anl, 2Pyr, 3Pyr, and 4Pyr); and 2Anl is the only radical cation with a rate coefficient distinctly different from its isomers. Quantum chemical calculations, using M06-2X-D3(0)/6-31++G(2df,p) geometries and DSD-PBEP86-NL/aug-cc-pVQZ energies, are deployed to rationalize reactivity trends based on the stability of prereactive complexes. The G3X-K method guides the assignment of product ions following adduct formation. The rate coefficient trend can be rationalized by a simple model based on the prereactive complex forward barrier height.

Heart development in two populations of Atlantic killifish (Fundulus heteroclitus) following exposure to a polycyclic aromatic hydrocarbon mixture

Historic industrial pollution of the Elizabeth River, Virginia resulted in polycyclic aromatic hydrocarbon (PAH) contamination in sediments. Atlantic killifish (Fundulus heteroclitus) inhabiting the Atlantic Wood (AW) industrial site adapted to complex PAH mixture at this Superfund site. Their embryos have proved highly resistant to cardiac abnormalities indicative of PAH toxicity. In this study, embryos spawned from adults collected at AW and King’s Creek (KC), a reference site, were exposed at 24 h post fertilization (hpf) to Elizabeth River Sediment Extract (ERSE), a complex PAH mixture, in a range of concentrations (0, 5.04, 50.45, 100.90, 151.35, or 252.25 µg/L total PAHs). Embryos were processed for histology at 144 hpf to enable evaluations of hearts at tissue and cellular levels. Morphometry and severity scoring were used to evaluate the extent of alterations. Unexposed embryos were similar in both populations. ERSE exposure resulted in multiple changes to hearts of KC embryos but not AW. Alterations were particularly evident in KC embryos exposed to concentrations above 1% ERSE (50.45 µg/L), which had thinner ventricular walls and larger pericardial edema. Individuals with moderate pericardial edema maintained arrangement and proximity of heart chambers, but changes were seen in ventricular myocytes. Severe pericardial edema was prevalent in exposed KC embryos and typically resulted in tube heart formation. Ventricles of tube hearts had very thin walls composed of small, basophilic cells and lacked trabeculae. Edematous pericardial fluid contained small amounts of proteinaceous material, as did controls, and was free of cells. This fluid was primarily unstained, suggesting water influx due to increased permeability. The use of histological approaches provided more specific detail for tissue and cellular effects in hearts of embryos exposed to PAHs and enabled understanding of potential links to later life effects of early life exposure.

Formation of Interstellar Complex Polycyclic Aromatic Hydrocarbons: Insights from Molecular Dynamics Simulations of Dehydrogenated Benzene

Abstract Small organic molecules are thought to provide building blocks for the formation of complex interstellar polycyclic aromatic hydrocarbons (PAHs). However, the underlying chemical mechanisms remain unclear, particularly concerning the role of interstellar dust. Using molecular dynamics, we simulate the chemical reaction between dehydrogenated benzene molecules in the gas phase or on the surface of an onion-like carbon nanoparticle (NP). The reaction leads to the formation of PAHs of complex structures. The size of the formed molecules is found to roughly increase with increasing temperature up to 800 K, and to be correlated with the level of dehydrogenation. Morphology analysis features the formation of large rings that contain up to 32 carbon atom at high temperature. Density functional theory (DFT) calculations are performed to search the fundamental energetic reaction pathways. The DFT results quantitatively confirm the correlation between the reactivity and the dehydrogenation level, and the formation of stable C-8 rings. Moreover, the nanostructures formed on the NP surface point to a possible layer-by-layer formation mechanism for interstellar fullerene and carbon onions.