Quantification of Monosaccharide Anhydrides by Liquid Chromatography Combined with Mass Spectrometry: Application to Aerosol Samples from an Urban and a Suburban Site Influenced by Small-Scale Wood Burning

Abstract Levels of the monosaccharide anhydride (MA) levoglucosan and its isomeric compounds galactosan and mannosan were quantified in the PM10 fraction (particulate matter ≤10 µm in aerodynamic diameter) of ambient aerosols from an urban (Oslo) and a suburban (Elverum) site in Norway, both influenced by small-scale wood burning. MAs are degradation products of cellulose and hemicellulose, and levoglucosan is especially emitted in high concentrations during pyrolysis and combustion of wood, making it a potential tracer of primary particles emitted from biomass burning. MAs were quantified using a novel high-performance liquid chromatography/ high-resolution mass spectrometry-time of flight method. This approach distinguishes between the isomeric compounds of MAs and benefits from the limited sample preparation required before analysis, and no extensive derivatization step is needed. The highest concentrations of levogucosan, galactosan, and mannosan (∑MA) were recorded in winter because of wood burning for residential heating (∑MAMAX = 1,240 ng m-3). This finding was substantiated by a relatively high correlation (R2 = 0.64) between the levoglucosan concentration and decreasing ambient temperature. At the suburban site, ∑MA accounted for 3.1% of PM10, whereas the corresponding level at the urban site was 0.6%. The mass size distribution of MAs associated with atmospheric aerosols was measured using a Berner cascade impactor. The size distribution was characterized with a single mode at 561 nm. Ninety-five percent of the mass concentration of the MAs was found to be associated with particles <2 µm. A preliminary attempt to estimate the contribution of wood burning to the mass concentration of PM10 in Oslo using levoglucosan as a tracer indicates that 24% comes from wood burning. This is approximately a factor of 2 lower than estimated by the AirQUIS dispersion model.

[1]  G. Klouda,et al.  Ambient impact of residential wood combustion in Elverum, Norway☆ , 1984 .

[2]  Christopher G. Nolte,et al.  Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles , 1999 .

[3]  R. Hillamo,et al.  Measuring the Size Distribution of Atmospheric Organic and Black Carbon Using Impactor Sampling Coupled with Thermal Carbon Analysis: Method Development and Uncertainties , 2002 .

[4]  Evaluation of a model for hourly spatial concentration distributions , 1993 .

[5]  J. I. Seeman,et al.  A model that distinguishes the pyrolysis of d-glucose, d-fructose, and sucrose from that of cellulose. Application to the understanding of cigarette smoke formation , 2003 .

[6]  John J. Langenfeld,et al.  PM-10 high-volume collection and quantitation of semi- and nonvolatile phenols, methoxylated phenols, alkanes, and polycyclic aromatic hydrocarbons from winter urban air and their relationship to wood smoke emissions , 1992 .

[7]  Glen R. Cass,et al.  Chemical composition of emissions from urban sources of fine organic aerosol , 1991 .

[8]  G. Cass,et al.  Chemical Characterization of Fine Particle Emissions from the Fireplace Combustion of Wood Types Grown in the Midwestern and Western United States , 2004 .

[9]  M. Claeys,et al.  Development of a gas chromatographic/ion trap mass spectrometric method for the determination of levoglucosan and saccharidic compounds in atmospheric aerosols. Application to urban aerosols. , 2002, Journal of mass spectrometry : JMS.

[10]  M. Claeys,et al.  Improved method for quantifying levoglucosan and related monosaccharide anhydrides in atmospheric aerosols and application to samples from urban and tropical locations. , 2002, Environmental science & technology.

[11]  B. Simoneit,et al.  Detecting organic tracers from biomass burning in the atmosphere. , 2001, Marine pollution bulletin.

[12]  M. Facchini,et al.  Soluble organic compounds in fog and cloud droplets: what have we learned over the past few years? , 2002 .

[13]  J. Schauer,et al.  Highly polar organic compounds present in wood smoke and in the ambient atmosphere. , 2001, Environmental science & technology.

[14]  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.

[15]  Christer Johansson,et al.  Chemical and physical characterization of emissions from birch wood combustion in a wood stove , 2002 .

[16]  Barbara J. Turpin,et al.  Investigation of organic aerosol sampling artifacts in the los angeles basin , 1994 .

[17]  M. Facchini,et al.  Water‐soluble organic compounds in biomass burning aerosols over Amazonia 1. Characterization by NMR and GC‐MS , 2002 .

[18]  J. Penner,et al.  Large contribution of organic aerosols to cloud-condensation-nuclei concentrations , 1993, Nature.

[19]  K. Yttri,et al.  Determination of monosaccharide anhydrides in atmospheric aerosols by use of high-performance liquid chromatography combined with high-resolution mass spectrometry. , 2005, Analytical chemistry.

[20]  M. Fraser,et al.  Using Levoglucosan as a Molecular Marker for the Long-Range Transport of Biomass Combustion Aerosols , 2000 .

[21]  T. Ramdahl Retene—a molecular marker of wood combustion in ambient air , 1983, Nature.

[22]  Michael J. Kleeman,et al.  Size and Composition Distribution of Fine Particulate Matter Emitted from Wood Burning, Meat Charbroiling, and Cigarettes , 1999 .

[23]  Eric M. Suuberg,et al.  Vapor Pressures and Enthalpies of Sublimation of d-Glucose, d-Xylose, Cellobiose, and Levoglucosan , 1999 .

[24]  R. Cary,et al.  Elemental Carbon-Based Method for Monitoring Occupational Exposures to Particulate Diesel Exhaust , 1996 .

[25]  M. Poore Levoglucosan in PM2.5 at the Fresno Supersite , 2002, Journal of the Air & Waste Management Association.

[26]  B. Simoneit,et al.  Biomass burning — a review of organic tracers for smoke from incomplete combustion , 2002 .