Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NOy) are also globally distributed, because NO formed in combustion processes is oxidized to NO2, HNO3, N2O5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NOy onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO2 or N2O5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO2), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

[1]  B. Finlayson‐Pitts,et al.  The heterogeneous hydrolysis of NO2 in laboratory systems and in outdoor and indoor atmospheres: An integrated mechanism , 2003 .

[2]  Charles J. Weschler,et al.  Indoor/outdoor concentrations and indoor surface accumulations of ionic substances , 1985 .

[3]  M. Rossi,et al.  Heterogeneous Kinetics of HONO on H2SO4 Solutions and on Ice: Activation of HCl , 1996 .

[4]  Franz Rohrer,et al.  Characterisation of the photolytic HONO-source in the atmosphere simulation chamber SAPHIR , 2004 .

[5]  G. Carmichael,et al.  Mineral dust is a sink for chlorine in the marine boundary layer , 2007 .

[6]  S. Rapsomanikis,et al.  The chemistry of gaseous acids in medieval churches in Cyprus , 2007 .

[7]  J. Baker.  An algorithm for the location of transition states , 1986 .

[8]  D. Tobias,et al.  Experimental and theoretical characterization of adsorbed water on self-assembled monolayers: understanding the interaction of water with atmospherically relevant surfaces. , 2009, The journal of physical chemistry. A.

[9]  P. Culot,et al.  A quasi-Newton algorithm for first-order saddle-point location , 1992 .

[10]  Michael Brauer,et al.  Indoor ozone and nitrogen dioxide: a potential pathway to the generation of nitrate radicals, dinitrogen pentoxide, and nitric acid indoors , 1992 .

[11]  Y. Miller,et al.  New experimental and theoretical approach to the heterogeneous hydrolysis of NO2: key role of molecular nitric acid and its complexes. , 2006, The journal of physical chemistry. A.

[12]  Mark S. Gordon,et al.  The Intrinsic Reaction Coordinate and the Rotational Barrier in Silaethylene , 1985 .

[13]  Brett M. Bode,et al.  MacMolPlt: a graphical user interface for GAMESS. , 1998, Journal of molecular graphics & modelling.

[14]  B. Finlayson‐Pitts.  Reaction of NO2 with NaCl and atmospheric implications of NOCl formation , 1983, Nature.

[15]  T. Helgaker.  Transition-state optimizations by trust-region image minimization , 1991 .

[16]  A. Ravishankara,et al.  High levels of nitryl chloride in the polluted subtropical marine boundary layer , 2008 .

[17]  M. Frankowski,et al.  Ionization and hydrolysis of dinitrogen pentoxide in low-temperature solids , 2001 .

[18]  Patricia A. Thiel,et al.  The interaction of water with solid surfaces: Fundamental aspects , 1987 .

[19]  L. Molina,et al.  Trace gas and particle emissions from domestic and industrial biofuel use and garbage burning in central Mexico , 2009 .

[20]  V. Vaida.  Spectroscopy of photoreactive systems: implications for atmospheric chemistry. , 2009, The journal of physical chemistry. A.

[21]  Thomas E. Graedel,et al.  Composite global emissions of reactive chlorine from anthropogenic and natural sources: Reactive Chlorine Emissions Inventory , 1999 .

[22]  J. Sodeau,et al.  A LOW-TEMPERATURE REFLECTION-ABSORPTION INFRARED SPECTROSCOPIC STUDY OF ULTRATHIN FILMS OF DINITROGEN TETROXIDE AND DINITROGEN PENTOXIDE ON GOLD FOIL , 1995 .

[23]  J. Last,et al.  Global atmospheric change: potential health effects of acid aerosol and oxidant gas mixtures. , 1991, Environmental health perspectives.

[24]  J. Hynes,et al.  A theoretical study of the reaction of ClONO{sub 2} with HCl on ice , 1999 .

[25]  T. Wallington,et al.  Identification and measurement of nitrous acid in an indoor environment , 1985 .

[26]  B. Finlayson‐Pitts,et al.  A Unique Method for Laboratory Quantification of Gaseous Nitrous Acid (HONO) Using the Reaction HONO + HCl → ClNO + H2O , 2000 .

[27]  Jörg Kleffmann,et al.  Daytime sources of nitrous acid (HONO) in the atmospheric boundary layer. , 2007, Chemphyschem : a European journal of chemical physics and physical chemistry.

[28]  Stephen E. Schwartz,et al.  Sea Salt Aerosol Production: Mechanisms, Methods, Measurements, and Models - A Critical Review , 2004 .

[29]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[30]  D. Blake,et al.  Airborne measurements of HCl from the marine boundary layer to the lower stratosphere over the North Pacific Ocean during INTEX-B , 2008 .

[31]  Kazuhiro Ishida,et al.  The intrinsic reaction coordinate. An ab initio calculation for HNC→HCN and H−+CH4→CH4+H− , 1977 .

[32]  Glenn Morrison,et al.  Interfacial chemistry in indoor environments. , 2008, Environmental science & technology.

[33]  K. Thompson,et al.  Hydrogen bonded complexes between nitrogen dioxide, nitric acid, nitrous acid and water with SiH3OH and Si(OH)4 , 2003 .

[34]  Mark S. Gordon,et al.  Interfacing Electronic Structure Theory with Dynamics , 1996 .

[35]  C. Cantrell,et al.  Reactions of nitrate radical and nitrogen oxide (N2O5) with molecular species of possible atmospheric interest , 1987 .

[36]  J. Stutz,et al.  Infrared Absorption Cross-Section Measurements for Nitrous Acid (HONO) at Room Temperature , 2000 .

[37]  B. Koel,et al.  Reactions of N2O4 with ice at low temperatures on the Au(111) surface , 1999 .

[38]  A. Guenther,et al.  The tropical forest and fire emissions experiment: laboratory fire measurements and synthesis of campaign data , 2008 .

[39]  M. Head‐Gordon,et al.  A fifth-order perturbation comparison of electron correlation theories , 1989 .

[40]  E. Grant,et al.  The vibrational structure of the NO2 cation , 1992 .

[41]  J. Stewart,et al.  Semi‐empirical calculations of molecular trajectories: Method and applications to some simple molecular systems , 1987 .

[42]  H. Bernhard Schlegel,et al.  An improved algorithm for reaction path following , 1989 .

[43]  Michael J. Frisch,et al.  A direct MP2 gradient method , 1990 .

[44]  Mark S. Gordon,et al.  Ab Initio Potential Energy Surface by Modified Shepard Interpolation: Application to the CH3+H2→CH4+H Reaction , 1998 .

[45]  M. Maccarini,et al.  Water at solid surfaces: A review of selected theoretical aspects and experiments on the subject , 2007, Biointerphases.

[46]  J. Seinfeld,et al.  Size‐resolved and chemically resolved model of atmospheric aerosol dynamics , 1998 .

[47]  J. Hynes,et al.  Heterogeneous reactions important in atmospheric ozone depletion: a theoretical perspective. , 2006, Accounts of chemical research.

[48]  Russell D. Johnson,et al.  NIST Computational Chemistry Comparison and Benchmark Database , 2005 .

[49]  Karol Kowalski,et al.  Efficient computer implementation of the renormalized coupled-cluster methods: The R-CCSD[T], R-CCSD(T), CR-CCSD[T], and CR-CCSD(T) approaches , 2002 .

[50]  J. Stutz,et al.  Inorganic chlorine and bromine in coastal New England air during summer , 2007 .

[51]  J. Orlando,et al.  The temperature dependence of the UV—visible absorption cross-sections of NOCl , 1992 .

[52]  Jennifer D. Schuttlefield,et al.  Photochemistry of adsorbed nitrate. , 2008, Journal of the American Chemical Society.

[53]  Y. Miller,et al.  Dynamics of proton recombination with NO3- anion in water clusters. , 2008, Physical chemistry chemical physics : PCCP.

[54]  Paul A. Makar,et al.  Chemical composition of surface films on glass windows and implications for atmospheric chemistry , 2005 .

[55]  J. Stutz,et al.  Atmospheric observations of enhanced NO2‐HONO conversion on mineral dust particles , 2003 .

[56]  K. Civerolo,et al.  Nitric acid photolysis on surfaces in low‐NOx environments: Significant atmospheric implications , 2003 .

[57]  M. Parrinello,et al.  At the water's edge: nitric acid as a weak acid. , 2007, Journal of the American Chemical Society.

[58]  Philip S. Anderson,et al.  Boundary layer physics over snow and ice , 2007 .

[59]  Xianliang Zhou,et al.  Photochemical production of nitrous acid on glass sample manifold surface , 2002 .

[60]  Y. Miller,et al.  Ionization of N2O4 in contact with water: mechanism, time scales and atmospheric implications. , 2009, Journal of the American Chemical Society.

[61]  Marilyn E. Jacox,et al.  The vibrational spectra of molecular ions isolated in solid neon. XI. NO+2, NO−2, and NO−3 , 1993 .

[62]  A. Neftel,et al.  Nitrous acid formation in the urban atmosphere: Gradient measurements of NO2 and HONO over grass in Milan, Italy , 2002 .

[63]  James N. Pitts,et al.  Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications , 1999 .

[64]  R. Prinn,et al.  Observations of high rates of NO 2 -HONO conversion in the nocturnal atmospheric boundary layer in Kathmandu, Nepal , 2009 .

[65]  D. Dabdub,et al.  Influence of sea-salt activated chlorine and surface-mediated renoxification on the weekend effect in the South Coast Air Basin of California , 2008 .

[66]  D. Donaldson,et al.  Where does acid hydrolysis take place? , 2009, Physical chemistry chemical physics : PCCP.

[67]  B. Finlayson‐Pitts.  The tropospheric chemistry of sea salt: a molecular-level view of the chemistry of NaCl and NaBr. , 2003, Chemical reviews.

[68]  J. Stephen Binkley,et al.  Theoretical models incorporating electron correlation , 2009 .

[69]  L. Barrie,et al.  Atmospheric reactive chlorine and bromine at the Great Salt Lake, Utah , 2002 .

[70]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[71]  M. Rossi.  Heterogeneous reactions on salts. , 2003, Chemical reviews.

[72]  R. Diamant.  The chemistry of building materials , 1970 .

[73]  Mark S. Gordon,et al.  A derivation of the frozen-orbital unrestricted open-shell and restricted closed-shell second-order perturbation theory analytic gradient expressions , 2003 .

[74]  C. Weschler,et al.  Deposition of Airborne Sulfate, Nitrate, and Chloride Salts as It Relates to Corrosion of Electronics , 1990 .

[75]  Shuzhi Wang,et al.  Theoretical study of the dissociation of nitric acid at a model aqueous surface. , 2007, The journal of physical chemistry. A.

[76]  Bruce E. Koel,et al.  IRAS Studies of NO2, N2O3, and N2O4 Adsorbed on Au(111) Surfaces and Reactions with Coadsorbed H2O , 1998 .

[77]  D. Jacob,et al.  Evidence of inorganic chlorine gases other than hydrogen chloride in marine surface air , 1993 .

[78]  M. Gordon,et al.  Ab initio reaction paths and direct dynamics calculations , 1989 .

[79]  F. E. Livingston,et al.  The reaction of gaseous N2O5 with solid NaCl at 298 K: Estimated lower limit to the reaction probability and its potential role in tropospheric and stratospheric chemistry , 1991 .

[80]  C. Zetzsch,et al.  Production and decay of ClNO2 from the reaction of gaseous N2O5 with NaCl solution: Bulk and aerosol experiments , 1997 .

[81]  V. Vaida,et al.  The influence of organic films at the air-aqueous boundary on atmospheric processes. , 2006, Chemical reviews.

[82]  Angela K. Wilson,et al.  Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton , 1993 .

[83]  T. L. Thompson,et al.  Chlorine activation near the midlatitude tropopause , 2007 .

[84]  B. Finlayson‐Pitts,et al.  Laboratory studies of potential mechanisms of renoxification of tropospheric nitric acid. , 2003, Environmental science & technology.

[85]  B. Hansmann,et al.  Water Catalysis of a Radical-Molecule Gas-Phase Reaction , 2007, Science.

[86]  Kwang S. Kim,et al.  Theory and applications of computational chemistry : the first forty years , 2005 .

[87]  D. Tobias,et al.  Experiments and simulations of ion-enhanced interfacial chemistry on aqueous NaCl aerosols , 2000, Science.

[88]  Mark S. Gordon,et al.  Algorithms and accuracy requirements for computing reaction paths by the method of steepest descent , 1988 .

[89]  Michel Dupuis,et al.  A dynamic reaction coordinate approach to ab initio reaction pathways: Application to the 1,5 hexadiene Cope rearrangement , 1990 .

[90]  David,et al.  Gaussian basis sets for use in correlated molecular calculations . Ill . The atoms aluminum through argon , 1999 .

[91]  A. D. da Silva,et al.  The isomerization of dinitrogen tetroxide: O2N-NO2 --> ONO-NO2. , 2007, The journal of physical chemistry. A.

[92]  Mark S. Gordon,et al.  DEVELOPMENTS IN PARALLEL ELECTRONIC STRUCTURE THEORY , 2007 .

[93]  D. Dabdub,et al.  Impact of chlorine emissions from sea-salt aerosol on coastal urban ozone. , 2003, Environmental science & technology.

[94]  J. Seinfeld,et al.  Secondary organic aerosol 1. Atmospheric chemical mechanism for production of molecular constituents , 2002 .

[95]  J. Stutz,et al.  Relative humidity dependence of HONO chemistry in urban areas , 2004 .

[96]  S. Rapsomanikis,et al.  Air pollutant emission rates and concentrations in medieval churches , 2008 .

[97]  Luria,et al.  DOAS measurements of tropospheric bromine oxide in mid-latitudes , 1999, Science.

[98]  William D. Gwinn,et al.  Normal Coordinates: General Theory, Redundant Coordinates, and General Analysis Using Electronic Computers , 1971 .