Physico-chemical characterization of SOA derived from catechol and guaiacol – a model substance for the aromatic fraction of atmospheric HULIS

Secondary organic aerosol (SOA) was produced from the aromatic precursors catechol and guaiacol by reaction with ozone in the presence and absence of simulated sunlight and humidity and investigated for its properties as a proxy for HUmic-LIke Substances (HULIS). Beside a small particle size, a relatively low molecular weight and typical optical features in the UV/VIS spectral range, HULIS contain a typical aromatic and/or olefinic chemical structure and highly oxidized functional groups within a high chemical diversity. Various methods were used to characterize the secondary organic aerosols obtained: Fourier transform infrared spectroscopy (FTIR) demonstrated the formation of several carbonyl containing functional groups as well as structural and functional differences between aerosols formed at different environmental conditions. UV/VIS spectroscopy of filter samples showed that the particulate matter absorbs far into the visible range up to more than 500 nm. Ultrahigh resolved mass spectroscopy (ICR-FT/MS) determined O/C-ratios between 0.3 and 1 and observed m/z ratios between 200 and 450 to be most abundant. Temperature-programmed-pyrolysis mass spectroscopy (TPP-MS) identified carboxylic acids and lactones/esters as major functional groups. Particle sizing using a condensation-nucleus-counter and differential-mobility-particle-sizer (CNC/DMPS) monitored the formation of small particles during the SOA formation process. Particle imaging, using field-emission-gun scanning electron microscopy (FEG-SEM), showed spherical particles, forming clusters and chains. We conclude that catechol and guaiacol are appropriate precursors for studies of the processing of aromatic SOA with atmospheric HULIS properties on the laboratory scale.

[1]  A. Hoffer,et al.  Molecular distributions of dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in biomass burning aerosols : implications for photochemical production and degradation in smoke layers , 2009 .

[2]  Evert Ljungström,et al.  The effect of temperature and water on secondary organic aerosol formation from ozonolysis of limonene, Δ 3 -carene and α-pinene , 2008 .

[3]  J. Ortega,et al.  Photooxidation of α-pinene at high relative humidity in the presence of increasing concentrations of NOx , 2008 .

[4]  M. Hallquist,et al.  Volatility of secondary organic aerosol , 2011 .

[5]  A. Dillner,et al.  ATR-FTIR characterization of organic functional groups and inorganic ions in ambient aerosols at a rural site , 2009 .

[6]  Time Resolved Infrared Spectroscopy of Formation and Processing of Secondary Organic Aerosol , 2010 .

[7]  T. Reponen,et al.  Design and Collection Efficiency of a New Electrostatic Precipitator for Bioaerosol Collection , 2002 .

[8]  M. Jenkin,et al.  Simulating the Formation of Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons , 2005 .

[9]  P. Wiesen,et al.  Heterogeneous conversion of NO 2 on secondary organic aerosol surfaces: A possible source of nitrous acid (HONO) in the atmosphere? , 2003 .

[10]  Erik Swietlicki,et al.  Organic aerosol and global climate modelling: a review , 2004 .

[11]  Kristen Averyt,et al.  Climate change 2007: Synthesis Report. Contribution of Working Group I, II and III to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change. Summary for Policymakers. , 2007 .

[12]  J. Williams,et al.  Natural abiotic formation of furans in soil. , 2010, Environmental science & technology.

[13]  R. Betts,et al.  Changes in Atmospheric Constituents and in Radiative Forcing. Chapter 2 , 2007 .

[14]  Yinon Rudich,et al.  Atmospheric HULIS : how humic-like are they ? A comprehensive and critical review , 2005 .

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

[16]  D. Sonntag.  Important new values of the physical constants of 1986, vapour pressure formulations based on the ITS-90, and psychrometer formulae , 1990 .

[17]  M. Kalberer,et al.  Product study of oleic acid ozonolysis as function of humidity , 2009 .

[18]  M. Andreae.  A New Look at Aging Aerosols , 2009, Science.

[19]  E. M. Perdue,et al.  High-precision frequency measurements: indispensable tools at the core of the molecular-level analysis of complex systems , 2007, Analytical and bioanalytical chemistry.

[20]  Cliff I. Davidson,et al.  Organic PM 2.5 : Fractionation by Polarity, FTIR Spectroscopy, and OM/OC Ratio for the Pittsburgh Aerosol , 2008 .

[21]  M. Kleeman,et al.  Open burning of agricultural biomass: Physical and chemical properties of particle-phase emissions , 2005 .

[22]  S. Cherenkevich,et al.  Ir spectra of preparations of ozonized pyrocatechin , 1998 .

[23]  W. Maenhaut,et al.  Chirality and the origin of atmospheric humic-like substances , 2009 .

[24]  I. Barnes,et al.  Rate coefficients for the gas-phase reaction of OH radicals with selected dihydroxybenzenes and benzoquinones , 2000 .

[25]  K. Jordan,et al.  Theoretical modeling of the OH stretch infrared spectrum of carboxylic acid dimers based on first-principles anharmonic couplings , 2003 .

[26]  Theoretical and Experimental Evaluation of a Portable Electrostatic TEM Sampler , 2007 .

[27]  F. J. Stevenson,et al.  Infrared spectra of humic acids and related substances , 1971 .

[28]  John H. Seinfeld,et al.  The formation, properties and impact of secondary organic aerosol: current and emerging issues , 2009 .

[29]  S. Gligorovski,et al.  Spectroscopic study of organic coatings on fine particles, exposed to ozone and simulated sunlight , 2010 .

[30]  J. Schauer,et al.  Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry , 2009 .

[31]  A. Limbeck,et al.  Organic acids in continental background aerosols , 1999 .

[32]  Qi Zhang,et al.  Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry , 2010 .

[33]  H. Mukai,et al.  Characterization of a humic acid-like brown substance in airborne particulate matter and tentative identification of its origin , 1986 .

[34]  C. Zetzsch,et al.  Direct Deposition of Aerosol Particles on an ATR Crystal for FTIR Spectroscopy Using an Electrostatic Precipitator , 2009 .

[35]  N. Sareen,et al.  Light-absorbing secondary organic material formed by glyoxal in aqueous aerosol mimics , 2009 .

[36]  R. Zenobi,et al.  Functional group analysis of high-molecular weight compounds in the water-soluble fraction of organic aerosols , 2007 .

[37]  G R Cass,et al.  Chemical characterization of fine particle emissions from fireplace combustion of woods grown in the northeastern United States. , 2001, Environmental science & technology.

[38]  E. Da̧bek-Złotorzyńska,et al.  Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy: organosulfates as photochemical smog constituents. , 2010, Analytical chemistry.

[39]  U. Baltensperger,et al.  Identification of Polymers as Major Components of Atmospheric Organic Aerosols , 2004, Science.

[40]  John H. Seinfeld,et al.  Atmospheric Photochemical Oxidation of Benzene: Benzene + OH and the Benzene−OH Adduct (Hydroxyl-2,4-cyclohexadienyl) + O2 , 1996 .

[41]  John H. Seinfeld,et al.  Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere , 2008 .

[42]  C. Zetzsch,et al.  Interactions of ozone with organic surface films in the presence of simulated sunlight: impact on wettability of aerosols. , 2008, Physical chemistry chemical physics : PCCP.

[43]  D. R. Worsnop,et al.  Evolution of Organic Aerosols in the Atmosphere , 2009, Science.

[44]  G. Láng,et al.  How many carboxyl groups does an average molecule of humic-like substances contain? , 2008 .

[45]  P. Schmitt‐Kopplin,et al.  Combined utilization of ion mobility and ultra-high-resolution mass spectrometry to identify multiply charged constituents in natural organic matter. , 2009, Rapid communications in mass spectrometry : RCM.

[46]  David John Lary,et al.  Carbonaceous aerosols and their potential role in atmospheric chemistry , 1999 .

[47]  C. Percival,et al.  Infrared spectroscopic studies of the heterogeneous reaction of ozone with dry maleic and fumaric acid aerosol particles. , 2009, Physical chemistry chemical physics : PCCP.

[48]  J. Behnke.  A New Look at Aging , 1975 .

[49]  G. Kiss,et al.  Chemical characterization of humic‐like substances (HULIS) formed from a lignin‐type precursor in model cloud water , 2004 .

[50]  A. Duarte,et al.  Spectroscopic study of the water-soluble organic matter isolated from atmospheric aerosols collected under different atmospheric conditions. , 2005 .

[51]  I. Barnes,et al.  Kinetics of the reaction of O3 with selected benzenediols , 2003 .

[52]  A. Dillner,et al.  A method to quantify organic functional groups and inorganic compounds in ambient aerosols using attenuated total reflectance FTIR spectroscopy and multivariate chemometric techniques , 2008 .

[53]  Y. Bedjanian,et al.  Aerosol formation yields from the reaction of catechol with ozone , 2009 .

[54]  U. Pöschl,et al.  Rainforest Aerosols as Biogenic Nuclei of Clouds and Precipitation in the Amazon , 2010, Science.

[55]  Yoshiteru Iinuma,et al.  Aerosol-chamber study of the α-pinene/O3 reaction: influence of particle acidity on aerosol yields and products , 2004 .

[56]  U. Baltensperger,et al.  Identification of organic acids in secondary organic aerosol and the corresponding gas phase from chamber experiments. , 2004, Analytical chemistry.

[57]  Christian Panse,et al.  Ultrahigh mass resolution and accurate mass measurements as a tool to characterize oligomers in secondary organic aerosols. , 2007, Analytical chemistry.

[58]  Hind A. Al-Abadleh,et al.  DRIFTS studies on the photodegradation of tannic acid as a model for HULIS in atmospheric aerosols. , 2009, Physical chemistry chemical physics : PCCP.

[59]  F. Keppler,et al.  Formation of chloroacetic acids from soil, humic acid and phenolic moieties. , 2003, Chemosphere.

[60]  G. Cass,et al.  Chemical characterzation of fine particle emissions from the fireplace combustion of woods grown in the Southern United States. , 2002, Environmental science & technology.

[61]  P. Schmitt‐Kopplin,et al.  Natural organic matter and the event horizon of mass spectrometry. , 2008, Analytical chemistry.

[62]  Jennifer D. Schuttlefield,et al.  Water uptake of humic and fulvic acid: measurements and modelling using single parameter Köhler theory , 2009 .

[63]  Corinne Le Quéré,et al.  Climate Change 2013: The Physical Science Basis , 2013 .

[64]  Yinon Rudich,et al.  Cloud Condensation Nuclei properties of model and atmospheric HULIS , 2006 .

[65]  Y. Maréchal,et al.  Infrared spectra of H-bonded systems: saturated carboxylic acid dimers , 1972 .

[66]  C. Zetzsch,et al.  A smog chamber for studies of the reactions of terpenes and alkanes with ozone and OH , 1988 .

[67]  R. Kurdi,et al.  In-situ Formation of Light-Absorbing Organic Matter in Cloud Water , 2003 .

[68]  H. Grothe,et al.  The heterogeneous reaction between soot and NO2 at elevated temperature , 2006 .

[69]  R. Kamens,et al.  Characterization of secondary aerosol from the photooxidation of toluene in the presence of NOx and 1-propene. , 2001, Environmental science & technology.

[70]  John H. Seinfeld,et al.  Secondary Organic Aerosol from the Photooxidation of Aromatic Hydrocarbons: Molecular Composition , 1997 .

[71]  D. Voisin,et al.  Comparison of analytical methods for Humic Like Substances (HULIS) measurements in atmospheric particles , 2009 .

[72]  F. J. Stevenson.  HUmus Chemistry Genesis, Composition, Reactions , 1982 .

[73]  C. Preston.  Humus Chemistry, Genesis, Composition and Reactions , 1995 .

[74]  P. Bloom,et al.  Diffuse Reflectance and Transmission Fourier Transform Infrared (DRIFT) Spectroscopy of Humic and Fulvic Acids , 1989 .

[75]  L. Treuel,et al.  Chemistry and Microphysics of Atmospheric Aerosol Surfaces: Laboratory Techniques and Applications , 2009 .

[76]  G. Socrates,et al.  Infrared Characteristic Group Frequencies , 1980 .

[77]  W. Arnott,et al.  Absorption Ångström coefficient, brown carbon, and aerosols: basic concepts, bulk matter, and spherical particles , 2010 .

[78]  John H. Seinfeld,et al.  Secondary organic aerosol formation from m-xylene, toluene, and benzene , 2007 .

[79]  A. Zimmerman,et al.  Transformation of catechol in the presence of a laccase and birnessite , 2006 .

[80]  Renato Zenobi,et al.  Time Resolved Infrared Spectroscopic Analysis of Aerosol Formed by Photo-Oxidation of 1,3,5-Trimethylbenzene and α-Pinene , 2005 .

[81]  K. Sakamoto,et al.  Determination of Dicarboxylic Acids and Levoglucosan in Fine Particles in the Kanto Plain, Japan, for Source Apportionment of Organic Aerosols , 2010 .