Characterization of simple saccharides and other organic compounds in atmospheric particulate matter and source apportionment using positive matrix factorization
Fraser, Matthew P.; Griffin, Robert J.
Doctor of Philosophy
Ambient particulate matter samples were collected at various sites in Texas, Arizona, and Austria from 2005 to 2009 to characterize the organic compositions and local PM sources. The primary biologically derived carbon sources, specifically the atmospheric entrainment of soil and associated biota and primary biological aerosol particles (PBAPs), are major sources contributing to ambient PM. This dissertation work proposes simple saccharides as well-suited tracers to characterize the contribution to ambient PM from these primary biologically derived carbon sources. Saccharide concentrations in ambient PM were determined from various locations and various seasons. Aerosol saccharide compounds displayed seasonal variations, inter-correlations, and size fractionations (fine vs. coarse) that were consistent between samples and that can be used to determine sources. The difference in aerosol saccharide concentrations and relative species abundances was reflective of different climate patterns and ecosystems. Selected saccharide compounds including an established marker (levoglucosan) and novel markers (glucose, sucrose, trehalose, mannitol, and arabitol) were used along with other markers to model the major source contributions to ambient PM using a positive matrix factorization (PMF) model. Major local PM sources were resolved at three Texas sites (San Augustine, Dallas, and Big Bend National Park) and one Arizona site (Higley), with two source factors enriched in the proposed novel saccharide markers that can be related to the primary biologically derived carbon sources. The contribution to PM from the saccharide-rich primary biological sources was estimated to range from 16% (remote area) to 36% (rural and suburban area) at the four sampling sites studied. Other PM sources identified by PMF included motor vehicles, secondary aerosol formation, meat cooking, biogenic wax, sea salt, crustal material, and road dust. To further characterize the primary biologically derived carbon sources, different soil and source samples representing PBAPs (plants and spores) were collected at Higley (AZ) to study their saccharide compositions in particle sizes equivalent to PM2.5 and PM10. It was found that the total measured non-levoglucosan saccharide content relative to PM mass in ambient aerosols (0.2% on average in PM2.5 and 0.11% in PM10) was much higher than the soil samples (<0.02% in both PM2.5 and PM10) but much lower than in the PBAP source samples (2% on average in plant PBAP samples and 16% in spore PBAP samples). The measured PBAP samples contained a concentration of sucrose and glucose that is consistent with the saccharide-rich source profiles resolved from ambient aerosol data analyzed by PMF while the measured soil samples did not. This can be interpreted as confirmation that PBAPs are an important PM source in additional to soil and associate biota at Higley, AZ. However, the saccharide levels in the measured PBAP samples were several orders of magnitude higher than the PMF results, suggesting that the ambient aerosol samples are a combination of high saccharide concentration PBAPs and lower saccharide concentration soils at Higley, AZ.
Atmospheric chemistry; Analytical chemistry; Environmental engineering