New insights into atmospheric sources and sinks of isocyanic acid, HNCO, from recent urban and regional observations

Isocyanic acid (HNCO) has only recently been measured in the ambient atmosphere, and many aspects of its atmospheric chemistry are still uncertain. HNCO was measured during three diverse field campaigns: California Nexus—Research at the Nexus of Air Quality and Climate Change (CalNex 2010) at the Pasadena ground site, Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT 2011) at the Boulder Atmospheric Observatory (BAO) in Weld County, CO, and Biofuel Crops emission of Ozone precursors intensive (BioCORN 2011), in a cornfield NW of Fort Collins, CO. Mixing ratios varied from below detection limit (~0.003 ppbv) to over 1.2 ppbv during a period when agricultural burning impacted the BAO Tower site. Urban areas, such as the CalNex 2010 Pasadena site, appear to have both primary (combustion) and secondary (photochemical) sources of HNCO, 50 ± 9%, and 33 ± 12%, respectively, while primary sources were responsible for the large mixing ratios of HNCO observed during the wintertime NACHTT study in suburban Colorado. Isocyanic acid during the BioCORN study in rural NE Colorado was closely correlated to ozone and therefore likely photochemically produced as a secondary product from amines or formamide. The removal of HNCO from the lower atmosphere is thought to be due to deposition, as common gas phase loss processes of photolysis and reactions with hydroxyl radicals, are slow. These ambient measurements are consistent with some HNCO deposition, which was evident at night at these surface sites.

[1]  J. Jimenez,et al.  Vertically resolved chemical characteristics and sources of submicron aerosols measured on a Tall Tower in a suburban area near Denver, Colorado in winter , 2013 .

[2]  M. Fiddler,et al.  Numerical modeling of cloud chemistry effects on isocyanic acid (HNCO) , 2013 .

[3]  J. Thornton,et al.  Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT): Overview of a wintertime air chemistry field study in the front range urban corridor of Colorado , 2013 .

[4]  Gang Lu,et al.  Measurements of gas phase acids in diesel exhaust: a relevant source of HNCO? , 2013, Environmental science & technology.

[5]  J. Seinfeld,et al.  The 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) field study , 2013 .

[6]  A. Wexler,et al.  Atmospheric amines – Part III: Photochemistry and toxicity , 2013 .

[7]  R. V. Morris,et al.  Acid sulfate alteration of fluorapatite, basaltic glass and olivine by hydrothermal vapors and fluids: Implications for fumarolic activity and secondary phosphate phases in sulfate‐rich Paso Robles soil at Gusev Crater, Mars , 2013 .

[8]  Jan Czerwinski,et al.  Effects of a combined Diesel particle filter-DeNOx system (DPN) on reactive nitrogen compounds emissions: a parameter study. , 2012, Environmental science & technology.

[9]  Elena Shevliakova,et al.  Separating agricultural and non-agricultural fire seasonality at regional scales , 2012 .

[10]  J. Lamarque,et al.  Isocyanic acid in a global chemistry transport model:tropospheric distribution, budget, and identification of regions with potential health impacts , 2012 .

[11]  J. Jimenez,et al.  Evaluation of Composition-Dependent Collection Efficiencies for the Aerodyne Aerosol Mass Spectrometer using Field Data , 2012 .

[12]  A. Weinheimer,et al.  Effects of aging on organic aerosol from open biomass burning smoke in aircraft and laboratory studies , 2011 .

[13]  D. Blake,et al.  The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010 , 2011 .

[14]  A. Wisthaler,et al.  Study of OH-initiated degradation of 2-aminoethanol , 2011 .

[15]  J. D. de Gouw,et al.  Evidence of rapid production of organic acids in an urban air mass , 2011 .

[16]  Jan Czerwinski,et al.  Reactive nitrogen compounds (RNCs) in exhaust of advanced PM–NOx abatement technologies for future diesel applications , 2011 .

[17]  I. R. Burling,et al.  Isocyanic acid in the atmosphere and its possible link to smoke-related health effects , 2011, Proceedings of the National Academy of Sciences.

[18]  Robert J. Yokelson,et al.  VOC identification and inter-comparison from laboratory biomass burning using PTR-MS and PIT-MS , 2011 .

[19]  A. Mellouki,et al.  Aspects of the atmospheric chemistry of amides. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[20]  I. R. Burling,et al.  Measurements of gas‐phase inorganic and organic acids from biomass fires by negative‐ion proton‐transfer chemical‐ionization mass spectrometry , 2010 .

[21]  I. R. Burling,et al.  Laboratory measurements of trace gas emissions from biomass burning of fuel types from the southeastern and southwestern United States , 2010 .

[22]  S. Montzka,et al.  Ozone variability and halogen oxidation within the Arctic and sub-Arctic springtime boundary layer , 2010 .

[23]  S. K. Akagi,et al.  Emission factors for open and domestic biomass burning for use in atmospheric models , 2010 .

[24]  I. R. Burling,et al.  Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions , 2010 .

[25]  S. Hazen,et al.  Carbamylation-Dependent Activation of T Cells: A Novel Mechanism in the Pathogenesis of Autoimmune Arthritis , 2010, The Journal of Immunology.

[26]  I. R. Burling,et al.  Measurements of gas-phase inorganic and organic acids in biomass fires by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) , 2009 .

[27]  M. Zahniser,et al.  Development of negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) for the measurement of gas-phase organic acids in the atmosphere , 2008 .

[28]  Martin Mohr,et al.  Organic aerosol mass spectral signatures from wood‐burning emissions: Influence of burning conditions and wood type , 2008 .

[29]  A. Stohl,et al.  Sources of particulate matter in the northeastern United States in summer: 2. Evolution of chemical and microphysical properties , 2008 .

[30]  E. Topol,et al.  Protein carbamylation links inflammation, smoking, uremia and atherogenesis , 2007, Nature Medicine.

[31]  Martin Mohr,et al.  Identification of the mass spectral signature of organic aerosols from wood burning emissions. , 2007, Environmental science & technology.

[32]  J. D. de Gouw,et al.  Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry. , 2007, Mass spectrometry reviews.

[33]  M. Andreae,et al.  Mass spectrometric analysis and aerodynamic properties of various types of combustion-related aerosol particles , 2006 .

[34]  A. Ravishankara,et al.  High resolution vertical distributions of NO 3 and N 2 O 5 through the , 2006 .

[35]  James M. Roberts,et al.  Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002 , 2005 .

[36]  O. Kröcher,et al.  An ammonia and isocyanic acid measuring method for soot containing exhaust gases , 2005 .

[37]  Lars-Erik Åmand,et al.  Formation of HNCO, HCN, and NH3 from the pyrolysis of bark and nitrogen-containing model compounds , 2004 .

[38]  N. W. Cant,et al.  The Reduction of NO by CO in the presence of water vapour on supported platinum catalysts : formation of isocyanic acid (HNCO) and ammonia , 2003 .

[39]  D. Jacob,et al.  In situ measurements of HCN and CH3CN over the Pacific Ocean: Sources, sinks, and budgets , 2003 .

[40]  M. Andreae,et al.  Emission of trace gases and aerosols from biomass burning , 2001 .

[41]  J. Drummond,et al.  Airborne intercomparison of vacuum ultraviolet fluorescence and tunable diode laser absorption measurements of tropospheric carbon monoxide , 2000 .

[42]  J. R. Pearson,et al.  Intercomparison of ground‐based NO y measurement techniques , 1998 .

[43]  A. Hansel,et al.  On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research , 1998 .

[44]  D. Trimm,et al.  The Formation of Isocyanic Acid (HNCO) by Reaction of NO, CO, and H2over Pt/SiO2and Its Hydrolysis on Alumina , 1996 .

[45]  Wing Tsang,et al.  Chemical Kinetic Data Base for Propellant Combustion. II. Reactions Involving CN, NCO, and HNCO , 1992 .

[46]  A. N. Strachan,et al.  Preparation and properties of isocyanic acid , 1982 .

[47]  G. L. Hutchinson,et al.  Ammonia and Amine Emissions from a Large Cattle Feedlot , 1982 .

[48]  James N. Pitts,et al.  Photooxidation of aliphatic amines under simulated atmospheric conditions: formation of nitrosamines, nitramines, amides, and photochemical oxidant , 1978 .

[49]  G. Kirby,et al.  Ultra-violet absorption spectrum of isocyanic acid , 1968 .

[50]  G. Stark,et al.  Reactions of the Cyanate Present in Aqueous Urea with Amino Acids and Proteins , 1960 .

[51]  E. Diczfalusy,et al.  On the Kinetics of the Decomposition of Cyanic Acid. , 1958 .

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