Combustion-derived substances in deep basins of Puget Sound: historical inputs from fossil fuel and biomass combustion

Reconstructions of 250 years historical inputs of two distinct types of black carbon (soot/graphitic black carbon (GBC) and char-BC) were conducted on sediment cores from two basins of the Puget Sound, WA. Signatures of polycyclic aromatic hydrocarbons (PAHs) were also used to support the historical reconstructions of BC to this system. Down-core maxima in GBC and combustion-derived PAHs occurred in the 1940s in the cores from the Puget Sound Main Basin, whereas in Hood Canal such peak was observed in the 1970s, showing basin-specific differences in inputs of combustion byproducts. This system showed relatively higher inputs from softwood combustion than the northeastern U.S. The historical variations in char-BC concentrations were consistent with shifts in climate indices, suggesting an influence of climate oscillations on wildfire events. Environmental loading of combustion byproducts thus appears as a complex function of urbanization, fuel usage, combustion technology, environmental policies, and climate conditions.     

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.     

Influence of combustion conditions on yields of solvent-extractable anhydrosugars and lignin phenols in chars: Implications for characterizations of biomass combustion residues

Anhydrosugars, such as levoglucosan and its isomers (mannosan, galactosan), as well as the solvent-extractable lignin phenols (methoxylated phenols) are thermal degradation products of cellulose/hemicellulose and lignin, respectively. These two groups of biomarkers are often used as unique tracers of combusted biomass inputs in diverse environmental media. However, detailed characterization of the relative proportion and signatures of these compounds in highly heterogeneous plant-derived chars are still scarce. Here we conducted a systematic study to investigate the yields of solvent-extractable anhydrosugars and lignin phenols in 25 lab-made chars produced from different plant materials under different combustion conditions. Solvent-extractable anhydrosugars and lignin phenols were only observed in chars formed below 350 °C and yields were variable across different combustion temperatures. The yields of mannosan (M) and galactosan (G) decreased more rapidly than those of levoglucosan (L) under increasing combustion severity (temperature and duration), resulting in variable L/M and L/(M + G) ratios, two diagnostic ratios often used for identification of combustion sources (e.g. hardwoods vs. softwoods vs. grasses). Our observations thus may provide an explanation for the wide ranges of values reported in the literature for these two ratios. On the other hand, the results of this study suggest that the ratios of the major solvent-extractable lignin phenols (vanillyls (V), syringyls (S), cinnamyls (C)) provide additional source reconstruction potential despite observed variations with combustion temperature. We thus propose using a property-property plot (L/M vs. S/V) as an improved means for source characterization of biomass combustion residues. The L/M-S/V plot has shown to be effective in environmental samples (soil organic matter, atmospheric aerosols) receiving substantial inputs of biomass combustion residues.