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Title: Temperature effect on phase state and reactivity controls atmospheric multiphase chemistry and transport of PAHs

Abstract

Polycyclic aromatic hydrocarbons like benzo(a)pyrene (BaP) in atmospheric particulate matter pose a threat to human health because of their high carcinogenicity. In the atmosphere, BaP is mainly degraded through a multiphase reaction with ozone, but the fate and atmospheric transport of BaP are poorly characterized. Earlier modeling studies used reaction rate coefficients determined in laboratory experiments at room temperature, which may overestimate/underestimate degradation rates when applied under atmospheric conditions. Moreover, the effects of diffusion on the particle bulk are not well constrained, leading to large discrepancies between model results and observations. We show how regional and global distributions and transport of BaP can be explained by a new kinetic scheme that provides a realistic description of the temperature and humidity dependence of phase state, diffusivity, and reactivity of BaP-containing particles. Low temperature and humidity can substantially increase the lifetime of BaP and enhance its atmospheric dispersion through both the planetary boundary layer and the free troposphere. The new scheme greatly improves the performance of multiscale models, leading to better agreement with observed BaP concentrations in both source regions and remote regions (Arctic), which cannot be achieved by less-elaborate degradation schemes (deviations by multiple orders of magnitude). Our results highlight themore » importance of considering temperature and humidity effects on both the phase state of aerosol particles and the chemical reactivity of particulate air pollutants.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [7]
  1. Max Planck Institute for Chemistry, Mainz (Germany)
  2. Max Planck Institute for Chemistry, Mainz (Germany); Univ. of California, Irvine, CA (United States)
  3. Jinan University, Guangzhou (China); Max Planck Institute for Chemistry, Mainz (Germany)
  4. Nanjing Univ. (China); Jiangsu Provincial Collaborative Innovation Center of Climate Change, Nanjing (China)
  5. Max Planck Institute for Chemistry, Mainz (Germany); Masaryk University, Brno (Czech Republic)
  6. Max Planck Institute for Chemistry, Mainz (Germany); Johannes Gutenberg University Mainz (Germany)
  7. Max Planck Institute for Chemistry, Mainz (Germany); Jinan University, Guangzhou (China)
Publication Date:
Research Org.:
Univ. of California, Irvine, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1499920
Grant/Contract Number:  
SC0018349
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 3; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES

Citation Formats

Mu, Qing, Shiraiwa, Manabu, Octaviani, Mega, Ma, Nan, Ding, Aijun, Su, Hang, Lammel, Gerhard, Pöschl, Ulrich, and Cheng, Yafang. Temperature effect on phase state and reactivity controls atmospheric multiphase chemistry and transport of PAHs. United States: N. p., 2018. Web. doi:10.1126/sciadv.aap7314.
Mu, Qing, Shiraiwa, Manabu, Octaviani, Mega, Ma, Nan, Ding, Aijun, Su, Hang, Lammel, Gerhard, Pöschl, Ulrich, & Cheng, Yafang. Temperature effect on phase state and reactivity controls atmospheric multiphase chemistry and transport of PAHs. United States. doi:10.1126/sciadv.aap7314.
Mu, Qing, Shiraiwa, Manabu, Octaviani, Mega, Ma, Nan, Ding, Aijun, Su, Hang, Lammel, Gerhard, Pöschl, Ulrich, and Cheng, Yafang. Wed . "Temperature effect on phase state and reactivity controls atmospheric multiphase chemistry and transport of PAHs". United States. doi:10.1126/sciadv.aap7314. https://www.osti.gov/servlets/purl/1499920.
@article{osti_1499920,
title = {Temperature effect on phase state and reactivity controls atmospheric multiphase chemistry and transport of PAHs},
author = {Mu, Qing and Shiraiwa, Manabu and Octaviani, Mega and Ma, Nan and Ding, Aijun and Su, Hang and Lammel, Gerhard and Pöschl, Ulrich and Cheng, Yafang},
abstractNote = {Polycyclic aromatic hydrocarbons like benzo(a)pyrene (BaP) in atmospheric particulate matter pose a threat to human health because of their high carcinogenicity. In the atmosphere, BaP is mainly degraded through a multiphase reaction with ozone, but the fate and atmospheric transport of BaP are poorly characterized. Earlier modeling studies used reaction rate coefficients determined in laboratory experiments at room temperature, which may overestimate/underestimate degradation rates when applied under atmospheric conditions. Moreover, the effects of diffusion on the particle bulk are not well constrained, leading to large discrepancies between model results and observations. We show how regional and global distributions and transport of BaP can be explained by a new kinetic scheme that provides a realistic description of the temperature and humidity dependence of phase state, diffusivity, and reactivity of BaP-containing particles. Low temperature and humidity can substantially increase the lifetime of BaP and enhance its atmospheric dispersion through both the planetary boundary layer and the free troposphere. The new scheme greatly improves the performance of multiscale models, leading to better agreement with observed BaP concentrations in both source regions and remote regions (Arctic), which cannot be achieved by less-elaborate degradation schemes (deviations by multiple orders of magnitude). Our results highlight the importance of considering temperature and humidity effects on both the phase state of aerosol particles and the chemical reactivity of particulate air pollutants.},
doi = {10.1126/sciadv.aap7314},
journal = {Science Advances},
number = 3,
volume = 4,
place = {United States},
year = {2018},
month = {3}
}

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Cited by: 20 works
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Figures / Tables:

Fig. 1. Fig. 1. : Kinetic scheme ROI-T. (A) First-ordermultiphase degradation rate coefficient k (s−1) for laboratory schemes of Pöschl et al. (4), Kahan et al. (22), Kwamena et al. (5), and Zhou et al. (11) (table S1) and the kinetic scheme ROI-T at 50 ppb O3. Vertical dashed line denotes 23°C.more » (B) Model framework of the multilayer kinetic scheme ROI-T. Red arrows show the reactions: O3 is decomposed and forms ROI in the gas sorption layer, BaP reacts with ROI between gas sorption and surface layer, and BaP reacts with O3 in the bulk. Green arrows show the RH/T-dependent mass transport: O3 from gas sorption to bulk layer, BaP from bulk to surface layer.« less

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