scholarly journals Impact of PAH photodissociation on the formation of small hydrocarbons in the Orion Bar and the horsehead PDRs

2020 ◽  
Vol 497 (2) ◽  
pp. 2327-2339 ◽  
Author(s):  
M S Murga ◽  
M S Kirsanova ◽  
A I Vasyunin ◽  
Ya N Pavlyuchenkov
Keyword(s):  
Gas Phase ◽  
Chemical Reactions ◽  
Aromatic Hydrocarbons ◽  
Laboratory Experiments ◽  
Acetylene Molecule ◽  
Physical Conditions ◽  
Polycyclic Aromatic ◽  
Photodissociation Regions ◽  
Acetylene Production ◽  
Phase Chemical

ABSTRACT We study whether polycyclic aromatic hydrocarbons (PAHs) can be a weighty source of small hydrocarbons in photodissociation regions (PDRs). We modelled the evolution of 20 specific PAH molecules in terms of dehydrogenation and destruction of the carbon skeleton under the physical conditions of two well-studied PDRs, the Orion Bar, and the Horsehead nebula that represent prototypical examples of PDRs irradiated by ‘high’ and ‘low’ ultraviolet radiation field. PAHs are described as microcanonical systems. The acetylene molecule is considered as the main carbonaceous fragment of the PAH dissociation, as it follows from laboratory experiments and theory. We estimated the rates of acetylene production in gas phase chemical reactions and compared them with the rates of the acetylene production through the PAH dissociation. It is found that the latter rates can be higher than the former rates in the Orion Bar at AV < 1 and also at AV > 3.5. In the Horsehead nebula, the chemical reactions provide more acetylene than the PAH dissociation. The produced acetylene participate in the reactions of the formation of small hydrocarbons (C2H, C3H, C3H+, C3H2, C4H). Acetylene production via the PAH destruction may increase the abundances of small hydrocarbons produced in gas phase chemical reactions in the Orion Bar only at AV > 3.5. In the Horsehead nebula, the contribution of PAHs to the abundances of the small hydrocarbons is negligible. We conclude that the PAHs are not a major source of small hydrocarbons in both PDRs except some locations in the Orion Bar.

scholarly journals Non-equilibrium interplay between gas–particle partitioning and multiphase chemical reactions of semi-volatile compounds: mechanistic insights and practical implications for atmospheric modeling of polycyclic aromatic hydrocarbons

2021 ◽  
Vol 21 (8) ◽  
pp. 6175-6198
Author(s):  
Jake Wilson ◽  
Ulrich Pöschl ◽  
Manabu Shiraiwa ◽  
Thomas Berkemeier
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Gas Phase ◽  
Chemical Reactions ◽  
Aromatic Hydrocarbons ◽  
Rate Coefficient ◽  
Chemical Transport ◽  
Time Step ◽  
Transport Models ◽  
Chemical Transport Models ◽  
Polycyclic Aromatic

Abstract. Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic air pollutants. The dispersion of PAHs in the atmosphere is influenced by gas–particle partitioning and chemical loss. These processes are closely interlinked and may occur at vastly differing timescales, which complicates their mathematical description in chemical transport models. Here, we use a kinetic model that explicitly resolves mass transport and chemical reactions in the gas and particle phases to describe and explore the dynamic and non-equilibrium interplay of gas–particle partitioning and chemical losses of PAHs on soot particles. We define the equilibration timescale τeq of gas–particle partitioning as the e-folding time for relaxation of the system to the partitioning equilibrium. We find this metric to span from seconds to hours depending on temperature, particle surface area, and the type of PAH. The equilibration time can be approximated using a time-independent equation, τeq≈1kdes+kads, which depends on the desorption rate coefficient kdes and adsorption rate coefficient kads, both of which can be calculated from experimentally accessible parameters. The model reveals two regimes in which different physical processes control the equilibration timescale: a desorption-controlled and an adsorption-controlled regime. In a case study with the PAH pyrene, we illustrate how chemical loss can perturb the equilibrium particulate fraction at typical atmospheric concentrations of O3 and OH. For the surface reaction with O3, the perturbation is significant and increases with the gas-phase concentration of O3. Conversely, perturbations are smaller for reaction with the OH radical, which reacts with pyrene on both the surface of particles and in the gas phase. Global and regional chemical transport models typically approximate gas–particle partitioning with instantaneous-equilibration approaches. We highlight scenarios in which these approximations deviate from the explicitly coupled treatment of gas–particle partitioning and chemistry presented in this study. We find that the discrepancy between solutions depends on the operator-splitting time step and the choice of time step can help to minimize the discrepancy. The findings and techniques presented in this work not only are relevant for PAHs but can also be applied to other semi-volatile substances that undergo chemical reactions and mass transport between the gas and particle phase.

Potential Contribution of Nutrients and Polycyclic Aromatic Hydrocarbons from the Creeks of Cootes Paradise Marsh

1996 ◽  
Vol 31 (3) ◽  
pp. 485-504 ◽  
Author(s):  
Patricia Chow-Fraser ◽  
Barb Crosbie ◽  
Douglas Bryant ◽  
Brian McCarry
Keyword(s):  
Aromatic Hydrocarbons ◽  
Laboratory Experiments ◽  
Dry Weight ◽  
Common Source ◽  
Potential Contribution ◽  
Nitrogen And Phosphorus ◽  
Engine Combustion ◽  
Polycyclic Aromatic ◽  
High Concentrations ◽  
Derivatives Of

Abstract During the summer of 1994, we compared the physical and nutrient characteristics of the three main tributaries of Cootes Paradise: Spencer, Chedoke and Borer’s creeks. On all sampling occasions, concentrations of CHL α and nutrients were always lowest in Borer’s Creek and highest in Chedoke Creek. There were generally 10-fold higher CHL α concentrations and 2 to 10 times higher levels of nitrogen and phosphorus in Chedoke Creek compared with Spencer Creek. Despite this, the light environment did not differ significantly between Spencer and Chedoke creeks because the low algal biomass in Spencer Creek was balanced by a relatively high loading of inorganic sediments from the watershed. Laboratory experiments indicated that sediments from Chedoke Creek released up to 10 µg/g of soluble phosphorus per gram (dry weight) of sediment, compared with only 2 µg/g from Spencer Creek. By contrast, sediment samples from Spencer Creek contained levels of polycyclic aromatic hydrocarbon that were as high as or higher than those from Chedoke Creek, and much higher than those found in Borer’s Creek. The distribution of normalized PAH concentrations suggests a common source of PAHs in all three tributaries, most likely automobile exhaust, since there were high concentrations of fluoranthene and pyrene, both of which are derivatives of engine combustion.

scholarly journals Study of passive sampling of polycyclic aromatic hydrocarbons in gas phase using Amberlite XAD resins as filling materials of semipermeable membranes

2013 ◽  
Vol 110 ◽  
pp. 494-500 ◽  
Author(s):  
Luis Gustavo T. dos Reis ◽  
Daniel Gallart-Mateu ◽  
Wagner F. Pacheco ◽  
Agustín Pastor ◽  
Miguel de la Guardia ◽  
...  
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Gas Phase ◽  
Aromatic Hydrocarbons ◽  
Passive Sampling ◽  
Semipermeable Membranes ◽  
Filling Materials ◽  
Polycyclic Aromatic ◽  
Xad Resins

Partitioning of unsubstituted Polycyclic Aromatic Hydrocarbons between surface sediments and the water column in the Brisbane River Estuary

1990 ◽  
Vol 41 (4) ◽  
pp. 443 ◽  
Author(s):  
SI Kayal ◽  
DW Connell
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Water Column ◽  
Aromatic Hydrocarbons ◽  
Partition Coefficients ◽  
Laboratory Experiments ◽  
River Estuary ◽  
Chemical Properties ◽  
Linear Relationships ◽  
Physico Chemical ◽  
Polycyclic Aromatic

In all, 23 sediment samples and 8 water column samples from the Brisbane River estuary, Queensland, Australia, were analysed for polycyclic aromatic hydrocarbons (PAHs) in order to assess the field partitioning behaviour of these hydrocarbons. Twelve PAHs, ranging in molecular weight from naphthalene to benzo[a]pyrene, were identified and quantified. Their partition coefficients, indexed to sediment organic carbon and lipid content, were calculated after filtering to remove particulates and making a calculated adjustment for colloids, or organic matter, in the water phase. In logarithmic form, the partition coefficients were related to the physico-chemical properties of the compounds (Kow, Sw, RRT) by relationships having a parabolic shape rather than being linear. However, compounds with log Kow values of less than 5.5 gave linear relationships comparable to, but distinctly different from, those obtained from laboratory experiments. It is suggested that field conditions have distinctive differences from laboratory experiments that do not allow the direct translation of laboratory-based relationships to the natural aquatic environment.

scholarly journals Variability of polycyclic aromatic hydrocarbons and their oxidative derivatives in wintertime Beijing, China

2019 ◽  
Vol 19 (13) ◽  
pp. 8741-8758 ◽  
Author(s):  
Atallah Elzein ◽  
Rachel E. Dunmore ◽  
Martyn W. Ward ◽  
Jacqueline F. Hamilton ◽  
Alastair C. Lewis
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Gas Phase ◽  
Aromatic Hydrocarbons ◽  
Total Concentration ◽  
Diagnostic Ratios ◽  
Strong Positive Correlation ◽  
Night Time ◽  
Naphthalic Anhydride ◽  
Positive Correlation ◽  
Polycyclic Aromatic

Abstract. Ambient particulate matter (PM) can contain a mix of different toxic species derived from a wide variety of sources. This study quantifies the diurnal variation and nocturnal abundance of 16 polycyclic aromatic hydrocarbons (PAHs), 10 oxygenated PAHs (OPAHs) and 9 nitrated PAHs (NPAHs) in ambient PM in central Beijing during winter. Target compounds were identified and quantified using gas chromatography–time-of-flight mass spectrometry (GC-Q-ToF-MS). The total concentration of PAHs varied between 18 and 297 ng m−3 over 3 h daytime filter samples and from 23 to 165 ng m−3 in 15 h night-time samples. The total concentrations of PAHs over 24 h varied between 37 and 180 ng m−3 (mean: 97±43 ng m−3). The total daytime concentrations during high particulate loading conditions for PAHs, OPAHs and NPAHs were 224, 54 and 2.3 ng m−3, respectively. The most abundant PAHs were fluoranthene (33 ng m−3), chrysene (27 ng m−3), pyrene (27 ng m−3), benzo[a]pyrene (27 ng m−3), benzo[b]fluoranthene (25 ng m−3), benzo[a]anthracene (20 ng m−3) and phenanthrene (18 ng m−3). The most abundant OPAHs were 9,10-anthraquinone (18 ng m−3), 1,8-naphthalic anhydride (14 ng m−3) and 9-fluorenone (12 ng m−3), and the three most abundant NPAHs were 9-nitroanthracene (0.84 ng m−3), 3-nitrofluoranthene (0.78 ng m−3) and 3-nitrodibenzofuran (0.45 ng m−3). ∑PAHs and ∑OPAHs showed a strong positive correlation with the gas-phase abundance of NO, CO, SO2 and HONO, indicating that PAHs and OPAHs can be associated with both local and regional emissions. Diagnostic ratios suggested emissions from traffic road and coal combustion were the predominant sources of PAHs in Beijing and also revealed the main source of NPAHs to be secondary photochemical formation rather than primary emissions. PM2.5 and NPAHs showed a strong correlation with gas-phase HONO. 9-Nitroanthracene appeared to undergo a photodegradation during the daytime and showed a strong positive correlation with ambient HONO (R=0.90, P < 0.001). The lifetime excess lung cancer risk for those species that have available toxicological data (16 PAHs, 1 OPAH and 6 NPAHs) was calculated to be in the range 10−5 to 10−3 (risk per million people ranges from 26 to 2053 cases per year).

Sign in / Sign up

Export Citation Format

Share Document