Sulfur speciation in individual aerosol particles

Sulfur aerosols play an important role in acid deposition and the Earth's energy balance. Important species in these aerosols include methanesulfonates, hydroxymethanesulfonates, sulfates, and sulfites. Because the relative amounts of these species indicate different sources and atmospheric processes, it is important to distinguish them in single-aerosol particles. To accomplish this task, we use rapid single-particle mass spectrometry (RSMS), a technique that permits individual particles to be analyzed in an online mode. Each sulfur species produces a characteristic set of ions in the mass spectra. In simulated marine and urban aerosols the relative amounts of methanesulfonic acid (MSA) and sodium hydroxymethanesulfonate (NaHMSA) in a single particle can be determined from peak area ratios in the mass spectra. Improved quantitation is possible by application of the classification and regression tree (CART) algorithm to distinguish the mass spectra of particles having different compositions. Factors that influence speciation include particle size, morphology, and laser fluence.

[1]  R. Dingenen,et al.  Laboratory and Modelling Studies of the Formation of a Stable Intermediate in the Night-Time Oxidation of DMS , 1993 .

[2]  M. Andreae,et al.  Determination of methanesulfonic acid and non-sea-salt sulfate in single marine aerosol particles , 1989 .

[3]  Daniel M. Murphy,et al.  On-line single-particle analysis by laser desorption mass spectrometry , 1991 .

[4]  M. Zahniser,et al.  The temperature dependence of mass accommodation of sulfur dioxide and hydrogen peroxide on aqueous surfaces , 1989 .

[5]  Methanesulfonic acid and non-sea-salt sulfate in pacific air: Regional and seasonal variations , 1986 .

[6]  M. Hoffmann,et al.  Kinetics and mechanism of the formation of hydroxymethanesulfonic acid at low pH , 1984 .

[7]  K. Prather,et al.  Real-time characterization of individual aerosol particles using time-of-flight mass spectrometry , 1994 .

[8]  A. Wexler,et al.  CHROMIUM SPECIATION IN AEROSOLS BY RAPID SINGLE-PARTICLE MASS SPECTROMETRY , 1995 .

[9]  J. Liley,et al.  Dimethylsulfide and Aerosol Measurements at Ross Island, Antarctica , 1993 .

[10]  E. Saltzman,et al.  Rate of Reaction of Methanesulfonic Acid, Dimethyl Sulfoxide, and Dimethyl Sulfone with Hydroxyl Radical in Aqueous Solution , 1989 .

[11]  B. Spengler,et al.  Laser-Induced Mass Analysis of Single Particles in the Airborne State , 1994 .

[12]  J. Collett,et al.  Behavior of S(IV) and Formaldehyde in a Chemically Heterogeneous Cloud. , 1995, Environmental science & technology.

[13]  J. Gras,et al.  Measurement of Dimethyl Sulfide, Sulfur Dioxide, Methane Sulfonic Acid and Non Sea Salt Sulfate at the Cape Grim Baseline Station , 1993 .

[14]  W. Hoppel.  Nucleation in the MSA-water vapor system , 1987 .

[15]  S. Schwartz,et al.  Seasonal, latitudinal, and secular variations in temperature trend: Evidence for influence of anthropogenic sulfate , 1993 .

[16]  D. Jacob,et al.  Chemical composition of fogwater collected along the California coast. , 1985, Environmental science & technology.

[17]  R. G. Pena,et al.  Atmospheric gas and particle measurements at a rural northeastern U.S. site , 1986 .

[18]  B. Heikes,et al.  Chemical mechanisms of acid generation in the troposphere , 1985, Nature.

[19]  J. Plane.  Gas-Phase Atmospheric Oxidation of Biogenic Sulfur Compounds: A Review , 1989 .

[20]  T. Bates,et al.  Regional and seasonal variations in the flux of oceanic dimethylsulfide to the atmosphere , 1987 .

[21]  Anthony S. Wexler,et al.  On-line chemical analysis of aerosols by rapid single-particle mass spectrometry , 1995 .

[22]  Leo Breiman,et al.  Classification and Regression Trees , 1984 .

[23]  P. Brimblecombe,et al.  The solubility of methanesulphonic acid and its implications for atmospheric chemistry , 1985 .

[24]  M. Andreae,et al.  Distribution of Biogenic Sulfur Compounds in the Remote Southern Hemisphere , 1989 .

[25]  J. W. Munger,et al.  Identification of Hydroxymethanesulfonate in Fog Water , 1986, Science.

[26]  Anthony S. Wexler,et al.  Quantitation of Ionic Species in Single Microdroplets by Online Laser Desorption/Ionization , 1994 .

[27]  R. Grieken,et al.  Laser microprobe mass spectrometric identification of sulfur species in single micrometer-size particles , 1984 .

[28]  W. Winiwarter,et al.  Phase-partitioning and chemical reactions of low molecular weight organic compounds in fog , 1992 .

[29]  P. Wine,et al.  Kinetics and mechanism of hydroxyl reactions with organic sulfides , 1986 .

[30]  Daniel M. Murphy,et al.  Laser Ionization Mass Spectroscopy of Single Aerosol Particles , 1995 .

[31]  R. Grieken,et al.  Study of inorganic ammonium compounds in individual marine aerosol particles by laser microprobe mass spectrometry , 1987 .