Determination of levoglucosan and its isomers in size fractions of aerosol standard reference materials

The present study tested the extraction efficiency and quantification reproducibility of anhydrosugars in a series of NIST SRMs using two extraction protocols and isotopically-labeled (d₇-levoglucosan) vs. chemically analogous (sedoheptulosan) surrogates. In both instances, levoglucosan concentrations in the different versions of the Washington, D.C. urban dust standard (SRM 1649, 1649a, 1649b, and RM 8785) were similar. The present test also showed that levoglucosan concentrations were not affected by long-term shelf storage of dry material. Variability of analyses were similar for both surrogates and averaged <5%. Surrogate recoveries were shown to average 103 ± 7% and 97 ± 7% for d₇-levoglucosan and sedoheptulosan, respectively. The choice of solvent was shown to affect recoveries the most (but not variability). Levoglucosan concentrations were either seriously underestimated or overestimated with ethyl acetate extraction when d₇-levoglucosan or sedoheptulosan was used as surrogate, respectively. These results point to the need to use some fraction of polar solvent (i.e. methanol) in the solvent mixture. Anhydrosugar concentrations in the urban dust from the Czech Republic (candidate SRMs 2786 and 2787) were characterized by 3- to 7-fold higher anhydrosugar concentrations than those observed in the Washington, D.C. urban dust. The internal anhydrosugar signatures (i.e. levoglucosan/mannosan ratio: L/M) confirm the predominance of biomass combustion sources in both SRM series with mixed inputs from hardwood and softwood combustion in the Washington, D.C. urban dust and a predominantly softwood source in the Prague urban dust. The uniform distribution of anhydrosugars, across the particle size distribution of both SRM series, confirms earlier studies that low temperature charred materials contribute significant inputs to atmospheric ultrafine particles with long atmospheric residence time and transport ranges.