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Mineral dust aerosols promote the formation of toxic nitropolycyclic aromatic compounds.

ABSTRACT: Atmospheric nitrated polycyclic aromatic hydrocarbons (NPAHs), which have been shown to have adverse health effects such as carcinogenicity, are formed in part through nitration reactions of their parent polycyclic aromatic hydrocarbons (PAHs) in the atmosphere. However, little is known about heterogeneous nitration rates of PAHs by gaseous NO2 on natural mineral substrates, such as desert dust aerosols. Herein by employing kinetic experiments using a flow reactor and surface analysis by Fourier transform infrared spectroscopy with pyridine adsorption, we demonstrate that the reaction is accelerated on acidic surfaces of mineral dust, particularly on those of clay minerals. In support of this finding, we show that levels of ambient particle-associated NPAHs in Beijing, China, significantly increased during heavy dust storms. These results suggest that mineral dust surface reactions are an unrecognized source of toxic organic chemicals in the atmosphere and that they enhance the toxicity of mineral dust aerosols in urban environments.

SUBMITTER: Kameda T

PROVIDER: S-EPMC4830986 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:This study seeks to understand the compositional details of N-containing aromatic compounds (NACs) emitted during biomass burning (BB) and their contribution to light-absorbing organic carbon (OC), also termed brown carbon (BrC). Three laboratory BB experiments were conducted with two U.S. pine forest understory fuels typical of those consumed during prescribed fires. During the experiments, submicron aerosol particles were collected on filter media and subsequently extracted with methanol and examined for their optical and chemical properties. Significant correlations (p < 0.05) were observed between BrC absorption and elemental carbon (EC)/OC ratios for individual burns data. However, the pooled experimental data indicated that the BB BrC absorption depends on more than the BB fire conditions as represented by the EC/OC ratio. Fourteen NAC formulas were identified in the BB samples, most of which were also observed in simulated secondary organic aerosol (SOA) from photo-oxidation of aromatic VOCs with NOX. However, the molecular structures associated with the identical NAC formula from BB and SOA are different. In this work, the identified NACs from BB are featured by methoxy and cyanate groups, and are predominately generated during the flaming phase. The mass concentrations of identified NACs were quantified using authentic and surrogate standards, and their contributions to bulk light absorption of solvent extractable OC were also calculated. The contributions of identified NACs to organic matter (OM) and BrC absorption were significantly higher in flaming-phase samples than those in smoldering-phase samples, and correlated with EC/OC ratio (p < 0.05) for both individual burns and pooled experimental data, indicating that the formation of NACs from BB largely depends on burn conditions. The average contributions of identified NACs to overall BrC absorption at 365 nm ranged from 0.087 ± 0.024 to 1.22 ± 0.54%, 3 - 10 times higher than their mass contributions to OM (0.023 ± 0.0089 to 0.18 ± 0.067%), so the NACs with light absorption identified in this work from BB are likely strong BrC chromophores. Further studies are warranted to identify more light-absorbing compounds to explain the unknown fraction (> 98%) of BB BrC absorption.

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Mineral dust aerosols promote the formation of toxic nitropolycyclic aromatic compounds.

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