Analysis of Sugars and Sugar Polyols in Atmospheric Aerosols by Chloride Attachment in Liquid Chromatography/Negative Ion Electrospray Mass Spectrometry

• Published in: Environmental science & technology 2007-04, Vol.41 (7), p.2459-2466
• Main Authors: Wan, Eric C. H, Yu, Jian Zhen
• Format: Article
• Language: English
• Subjects: Aerosols; Aerosols - chemistry; Analysis methods; Analytical chemistry; Applied sciences; Atmosphere - chemistry; Atmospheric aerosols; Atmospheric pollution; Carbohydrates - analysis; Chemistry; Chemistry Techniques, Analytical - methods; Chlorides - chemistry; Chlorine; Chromatographic methods and physical methods associated with chromatography; Chromatography; Chromatography, Liquid - methods; Earth, ocean, space; Exact sciences and technology; External geophysics; Geophysics. Techniques, methods, instrumentation and models; Hong Kong; Ions; Mass spectrometry; Meteorology; Other chromatographic methods; Particles and aerosols; Pollution; Polymers - analysis; Principal components analysis; Scientific imaging; Spectrometry, Mass, Electrospray Ionization - methods; Sugar
• ISSN: 0013-936X; 1520-5851
• DOI: 10.1021/es062390g

Sugars and sugar polyols are relatively abundant groups of water-soluble constituents in atmospheric aerosols. This paper describes a method that uses liquid chromatography−mass spectrometry (LC−MS) to analyze sugars and sugar polyols in atmospheric aerosols, ranging from C3 sugar alcohols to trisaccharides. Postcolumn addition of chloroform in acetonitrile was found to greatly enhance ionization of these compounds by forming chloride adduct ions in the negative-ion mode using electrospray ionization. A gradient elution program starting at 5%:95% H2O/acetonitrile and ending at 30%:70% H2O/acetonitrile provides baseline separations of the sugars and sugar polyols on an amino-based carbohydrate column. The detection limits based on quantification of [M + 35Cl]- adduct ions were in the order of 0.1 μM. By eliminating the need for derivatization, this LC−MS based method provides a simpler alternative method to the commonly used and more laborious gas-chromatography based methods. It also has an additional advantage of being able to quantify trisaccharide sugars. The method was applied to analyze 30 ambient samples of fine particulate matter collected at a site away from urban centers in Hong Kong. The sugar compounds positively identified and detected in the ambient samples included four sugar alcohols (glycerol, erythritol, xylitol, and mannitol), three monosacchride sugars (xylose, fructose, and glucose), two disaccharides (sucrose, trehalose), two trisaccharides (melezitose, raffinose), and one anhydrosugar (levoglucosan). The sum of these sugar and sugar polyol compounds ranged from 38 to 1316 ng m-3, accounting for an average of 1.3% organic carbon mass. Through the use of a principal component analysis of the ambient measurements, the mono- to trisaccharide sugars and C3−C5 sugar polyols were identified to be mainly associated with soil/soil microbiota while the anhydrosugar (levoglucosan) was associated with biomass burning.