Ammonium deficiency caused by heterogeneous reactions during a super Asian dust episode

Mineral dust particles exert profound impacts on air quality, visibility, and ocean biogeochemistry. Interactions between dust particles and other anthropogenic pollutants modify not only the size spectrum and morphology but also physicochemical properties of dust particles, thereby affecting their radiative properties and ability to act as cloud condensation nuclei and in turn their impact on climate. Here we report field observations on the surface chemical transformations in a super Asian dust plume captured in coastal areas of China and the adjacent marginal seas. The dust plume showed enhanced concentrations of sulfate, nitrate, and calcium along with a decrease in ammonium. The percentages of total Ca in water‐soluble form increased from an intrinsic value of ~5% to 25–40% at four stations along the path of the dust plume. From these increases, we estimated the extent to which carbonate was modified by heterogeneous reactions and calculated that the enhanced sulfate and nitrate could account for 40–60% of the observed concentrations. Our observation suggests that the formation of ammonium sulfate via the H2SO4‐NH3‐H2O ternary system was impeded by heterogeneous reactions in the marine boundary layer when dust loads exceeded a certain threshold. A conceptual model is proposed to elucidate the heterogeneous reactions during the super Asian dust event and their impacts on atmospheric chemistry.

[1]  Renjian Zhang,et al.  Chemical characterization and source apportionment of PM 2 . 5 in Beijing : seasonal perspective , 2013 .

[2]  Chung-Chi Chen,et al.  A super Asian dust storm over the East and South China Seas: Disproportionate dust deposition , 2013 .

[3]  Athanasios Nenes,et al.  Implementation of dust emission and chemistry into the Community Multiscale Air Quality modeling system and initial application to an Asian dust storm episode , 2012 .

[4]  J. D. de Gouw,et al.  Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget. , 2012, Environmental science & technology.

[5]  Zifa Wang,et al.  Mixing of Asian mineral dust with anthropogenic pollutants over East Asia: a model case study of a super-duststorm in March 2010 , 2012 .

[6]  Dongho Shin,et al.  Record heavy mineral dust outbreaks over Korea in 2010: Two cases observed with multiwavelength aerosol/depolarization/Raman‐quartz lidar , 2012 .

[7]  Renjian Zhang,et al.  Investigation of direct radiative effects of aerosols in dust storm season over East Asia with an online coupled regional climate-chemistry-aerosol model , 2012 .

[8]  Jinhua Tao,et al.  Air quality modeling for a strong dust event in East Asia in March 2010 , 2012 .

[9]  R. Sullivan,et al.  Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars , 2010, Proceedings of the National Academy of Sciences.

[10]  G. Gong,et al.  Effects of acidic processing, transport history, and dust and sea salt loadings on the dissolution of iron from Asian dust , 2010 .

[11]  Yasunobu Iwasaka,et al.  Asian dust particles converted into aqueous droplets under remote marine atmospheric conditions , 2010, Proceedings of the National Academy of Sciences.

[12]  S. Liu,et al.  High wintertime particulate matter pollution over an offshore island (Kinmen) off southeastern China: An overview , 2010 .

[13]  G. Gong,et al.  Sources, solubility, and dry deposition of aerosol trace elements over the East China Sea , 2010 .

[14]  Kan Huang,et al.  Mixing of Asian dust with pollution aerosol and the transformation of aerosol components during the dust storm over China in spring 2007 , 2010 .

[15]  Kan Huang,et al.  Source, long‐range transport, and characteristics of a heavy dust pollution event in Shanghai , 2010 .

[16]  V. Grassian,et al.  Simulated atmospheric processing of iron oxyhydroxide minerals at low pH: Roles of particle size and acid anion in iron dissolution , 2010, Proceedings of the National Academy of Sciences.

[17]  J. Prospero,et al.  Trends in the solubility of iron in dust‐dominated aerosols in the equatorial Atlantic trade winds: Importance of iron speciation and sources , 2010 .

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

[19]  A. Weinheimer,et al.  Observations of heterogeneous reactions between Asian pollution and mineral dust over the Eastern North Pacific during INTEX-B , 2009 .

[20]  B. Finlayson‐Pitts Reactions at surfaces in the atmosphere: integration of experiments and theory as necessary (but not necessarily sufficient) for predicting the physical chemistry of aerosols. , 2009, Physical chemistry chemical physics : PCCP.

[21]  B. d'Anna,et al.  Photochemistry of mineral dust surface as a potential atmospheric renoxification process , 2009 .

[22]  Tao Wang,et al.  Summertime PM 2.5 ionic species in four major cities of China: nitrate formation in an ammonia-deficient atmosphere , 2008 .

[23]  David M. Cwiertny,et al.  Chemistry and photochemistry of mineral dust aerosol. , 2008, Annual review of physical chemistry.

[24]  Zifa Wang,et al.  Mixing of mineral with pollution aerosols in dust season in Beijing: Revealed by source apportionment study , 2008 .

[25]  M. Rossi Evaluated kinetic and photochemical data for atmospheric chemistry , 2010 .

[26]  S. Liu,et al.  Water‐soluble species in the marine aerosol from the northern South China Sea: High chloride depletion related to air pollution , 2007 .

[27]  J. Ji,et al.  Dolomite as a tracer for the source regions of Asian dust , 2007 .

[28]  C. Wagner,et al.  The interaction of N 2 O 5 with mineral dust: aerosol flow tube and Knudsen reactor studies , 2007 .

[29]  V. Grassian,et al.  Heterogeneous interactions of calcite aerosol with sulfur dioxide and sulfur dioxide-nitric acid mixtures. , 2007, Physical chemistry chemical physics : PCCP.

[30]  C. Usher,et al.  Reactions of sulfur dioxide on calcium carbonate single crystal and particle surfaces at the adsorbed water carbonate interface. , 2007, Physical chemistry chemical physics : PCCP.

[31]  C. Zender,et al.  Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions , 2007 .

[32]  M. Chin,et al.  Characterization of Asian Dust during ACE-Asia , 2006 .

[33]  Y. H. Zhang,et al.  Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate , 2006 .

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

[35]  Y. Balkanski,et al.  Interaction of mineral dust with gas phase nitric acid and sulfur dioxide during the MINATROC II field campaign: First estimate of the uptake coefficient from atmospheric data , 2005 .

[36]  Yinon Rudich,et al.  Direct observation of completely processed calcium carbonate dust particles. , 2005, Faraday discussions.

[37]  J. Lelieveld,et al.  Observations and model calculations of trace gas scavenging in a dense Saharan dust plume during MINATROC , 2005 .

[38]  A. Nenes,et al.  Dust and pollution: A recipe for enhanced ocean fertilization? , 2005 .

[39]  David G. Streets,et al.  Impacts of dust on regional tropospheric chemistry during the ACE‐Asia experiment: A model study with observations , 2004 .

[40]  Paolo Bonasoni,et al.  Aerosol-ozone correlations during dust transport episodes , 2004 .

[41]  B. Finlayson‐Pitts,et al.  The photochemical production of HONO during the heterogeneous hydrolysis of NO2 , 2004 .

[42]  Philip B. Russell,et al.  ACE-ASIA Regional Climatic and Atmospheric Chemical Effects of Asian Dust and Pollution , 2004 .

[43]  L. Horowitz,et al.  Impact of air pollution on wet deposition of mineral dust aerosols , 2004 .

[44]  Henry E. Fuelberg,et al.  Uptake of nitrate and sulfate on dust aerosols during TRACE‐P , 2003 .

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

[46]  A. Nenes,et al.  Iron mobilization in mineral dust: Can anthropogenic SO2 emissions affect ocean productivity? , 2003 .

[47]  C. Timmreck,et al.  Heterogeneous nucleation as a potential sulphate‐coating mechanism of atmospheric mineral dust particles and implications of coated dust on new particle formation , 2003 .

[48]  R. A. Cox,et al.  Hydrolysis of N2O5 on sub-micron mineral salt aerosols , 2003 .

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

[50]  Vicki H. Grassian,et al.  The transformation of solid atmospheric particles into liquid droplets through heterogeneous chemistry: Laboratory insights into the processing of calcium containing mineral dust aerosol in the troposphere , 2003 .

[51]  G. Chenc,et al.  Iron Mobilization in Mineral Dust : Can Anthropogenic SO 2 Emissions Affect Ocean Productivity ? , 2003 .

[52]  C. Usher,et al.  A laboratory study of the heterogeneous uptake and oxidation of sulfur dioxide on mineral dust particles , 2002 .

[53]  Russ E. Davis,et al.  Robotic Observations of Dust Storm Enhancement of Carbon Biomass in the North Pacific , 2002, Science.

[54]  V. Grassian Chemical Reactions of Nitrogen Oxides on the Surface of Oxide, Carbonate, Soot, and Mineral Dust Particles: Implications for the Chemical Balance of the Troposphere , 2002 .

[55]  G. Carmichael,et al.  Gas-Particle Partitioning of Nitric Acid Modulated by Alkaline Aerosol , 2001 .

[56]  Sung-Nam Oh,et al.  Chemical composition and source signature of spring aerosol in Seoul, Korea , 2001 .

[57]  A. Goodman,et al.  A laboratory study of the heterogeneous reaction of nitric acid on calcium carbonate particles , 2000 .

[58]  Zifa Wang,et al.  A deflation module for use in modeling long‐range transport of yellow sand over East Asia , 2000 .

[59]  J. Hemminger,et al.  Physical Chemistry of Airborne Sea Salt Particles and Their Components , 2000 .

[60]  J. Lelieveld,et al.  Airborne observations of dust aerosol over the North Atlantic Ocean during ACE-2: Indications for heterogeneous ozone destruction , 2000 .

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

[62]  D. Jacob Heterogeneous chemistry and tropospheric ozone , 2000 .

[63]  A. Wexler,et al.  Formation of nitrate and non-sea-salt sulfate on coarse particles , 1999 .

[64]  M. Andreae,et al.  Non‐sea‐salt sulfate, methanesulfonate, and nitrate aerosol concentrations and size distributions at Cape Grim, Tasmania , 1999 .

[65]  Daizhou Zhang,et al.  Nitrate and sulfate in individual Asian dust-storm particles in Beijing, China in Spring of 1995 and 1996 , 1999 .

[66]  J. Prospero,et al.  Variations in the size distribution of non‐sea‐salt sulfate aerosol in the marine boundary layer at Barbados: Impact of African dust , 1998 .

[67]  G. Stenchikov,et al.  The impact of aerosols on solar ultraviolet radiation and photochemical smog. , 1997, Science.

[68]  J. Prospero,et al.  Diel variability of soluble Fe(II) and soluble total Fe in North African dust in the trade winds at Barbados , 1997 .

[69]  Edward J. Carpenter,et al.  Trichodesmium, a Globally Significant Marine Cyanobacterium , 1997 .

[70]  A. R. Ravishankara,et al.  Heterogeneous and Multiphase Chemistry in the Troposphere , 1997 .

[71]  J. Lelieveld,et al.  Role of mineral aerosol as a reactive surface in the global troposphere , 1996 .

[72]  A. Lacis,et al.  The influence on climate forcing of mineral aerosols from disturbed soils , 1996, Nature.

[73]  H. Naruse,et al.  X-ray spectrometry of individual Asian dust-storm particles over the Japanese islands and the North Pacific Ocean , 1990 .

[74]  M. Andreae,et al.  Internal Mixture of Sea Salt, Silicates, and Excess Sulfate in Marine Aerosols , 1986, Science.

[75]  Z. A. Trapeznikova On the Interaction of , 1959 .

[76]  Seongryong Kim,et al.  American Geophysical Union. All Rights Reserved. Evidence of Volatile-Induced Melting , 2022 .