Mineral dust and NOx promote the conversion of SO2 to sulfate in heavy pollution days

Haze in China has been increasing in frequency of occurrence as well as the area of the affected region. Here, we report on a new mechanism of haze formation, in which coexistence with NOx can reduce the environmental capacity for SO2, leading to rapid conversion of SO2 to sulfate because NO2 and SO2 have a synergistic effect when they react on the surface of mineral dust. Monitoring data from five severe haze episodes in January of 2013 in the Beijing-Tianjin-Hebei regions agreed very well with the laboratory simulation. The combined air pollution of motor vehicle exhaust and coal-fired flue gases greatly reduced the atmospheric environmental capacity for SO2, and the formation of sulfate was found to be a main reason for the growth of fine particles, which led to the occurrence of haze. These results indicate that the impact of motor vehicle exhaust on the atmospheric environment might be underestimated.

[1]  W. B. Whalley,et al.  Rock glaciers and protalus landforms: Analogous forms and ice sources on Earth and Mars , 2003 .

[2]  Q. Ma,et al.  Synergistic effect between NO2 and SO2 in their adsorption and reaction on gamma-alumina. , 2008, The journal of physical chemistry. A.

[3]  X. Zhao,et al.  Analysis of a winter regional haze event and its formation mechanism in the North China Plain , 2013 .

[4]  P. Kasibhatla,et al.  A three-dimensional global model investigation of seasonal variations in the atmospheric burden of anthropogenic , 1997 .

[5]  P. Crutzen,et al.  Anthropogenic influence on the distribution of tropospheric sulphate aerosol , 1992, Nature.

[6]  Ting Yang,et al.  Formation and evolution mechanism of regional haze: a case study in the megacity Beijing, China , 2012 .

[7]  T. Berntsen,et al.  A global model of the coupled sulfur/oxidant chemistry in the troposphere: The sulfur cycle , 2004 .

[8]  L. Pirjola,et al.  Stable sulphate clusters as a source of new atmospheric particles , 2000, Nature.

[9]  E. M. Jones Chamber Process Manufacture of Sulfuric Acid , 1950 .

[10]  G. Sarwar,et al.  Potential impacts of two SO2 oxidation pathways on regional sulfate concentrations: Aqueous-phase oxidation by NO2 and gas-phase oxidation by Stabilized Criegee Intermediates , 2013 .

[11]  Min Hu,et al.  Nucleation and growth of nanoparticles in the atmosphere. , 2012, Chemical reviews.

[12]  S. Pandis,et al.  Removal of sulphur from the marine boundary layer by ozone oxidation in sea-salt aerosols , 1992, Nature.

[13]  Q. Ma,et al.  Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol. , 2012, Physical chemistry chemical physics : PCCP.

[14]  J. Hao,et al.  The remarkable effect of FeSO4 seed aerosols on secondary organic aerosol formation from photooxidation of α-pinene/NOx and toluene/NOx , 2012 .

[15]  A. Nowak,et al.  Mineral dust photochemistry induces nucleation events in the presence of SO2 , 2012, Proceedings of the National Academy of Sciences.

[16]  Q. Ma,et al.  In situ DRIFTS study of hygroscopic behavior of mineral aerosol. , 2010, Journal of environmental sciences.

[17]  K. Prather,et al.  Direct observations of the atmospheric processing of Asian mineral dust , 2006 .

[18]  M. Kulmala How Particles Nucleate and Grow , 2003, Science.

[19]  P. Hoppe,et al.  Enhanced Role of Transition Metal Ion Catalysis During In-Cloud Oxidation of SO2 , 2013, Science.

[20]  Dongfang Wang,et al.  Characterization of soil dust aerosol in China and its transport and distribution during 2001 ACE‐Asia: 1. Network observations , 2003 .

[21]  Qi Zhang,et al.  An Aerosol Chemical Speciation Monitor (ACSM) for Routine Monitoring of the Composition and Mass Concentrations of Ambient Aerosol , 2011 .

[22]  C. Usher,et al.  Reactions on mineral dust. , 2003, Chemical reviews.

[23]  Chunsheng Zhao,et al.  A review of atmospheric chemistry research in China: Photochemical smog, haze pollution, and gas-aerosol interactions , 2012, Advances in Atmospheric Sciences.

[24]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1997 .

[25]  T. Petäjä,et al.  A new atmospherically relevant oxidant of sulphur dioxide , 2012, Nature.

[26]  E. R. Allen,et al.  The Sulfur Cycle , 1972, Science.

[27]  H. Sievering,et al.  Heterogeneous and homogeneous oxidation of SO2 in the remote marine atmosphere , 1991 .

[28]  C. Land,et al.  A comparison of large-scale atmospheric sulphate aerosol models (COSAM): overview and highlights , 2001 .

[29]  J. Hao,et al.  Effect of mineral dust on secondary organic aerosol yield and aerosol size in α-pinene/NOx photo-oxidation , 2013 .

[30]  P. Crutzen,et al.  Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry , 1997 .

[31]  A. Laskin,et al.  Reactions at Interfaces As a Source of Sulfate Formation in Sea-Salt Particles , 2003, Science.

[32]  D. Jacob,et al.  Impact of mineral dust on nitrate, sulfate, and ozone in transpacific Asian pollution plumes , 2009 .

[33]  J. Xin,et al.  Mechanism for the formation of the January 2013 heavy haze pollution episode over central and eastern China , 2014 .