Sensitivity of a molecular marker based positive matrix factorization model to the number of receptor observations

To investigate the impact of the number of observations on molecular marker-based positive matrix factorization (MM-PMF) source apportionment models, daily PM2.5 samples were collected in East St. Louis, IL from April 2002 through May 2003. The samples were analyzed for daily 24-h average concentrations of elemental and organic carbon, trace elements, and speciated particle-phase organic compounds. A total of 273 sets of observations were used in the model and consisted of all valid sets of observations from the year long data set minus one sixth of the measurements, which were collected every 6th day and were analyzed by different chemical analysis techniques. In addition to the base case of 273 samples, systematic subsets of the data set were analyzed by PMF. These subsets of data included 50% of the observations (135-138 days), 33% of the observations (90-92 days) and 20% of the observations (52-56 days). In addition, model runs were also examined that used 48-h, 72-h, 6-day, and weekly average concentrations as model inputs. All MM-PMF model runs were processed following the same procedures to explore the stability of the source attribution results. Consistent with previous MM-PMF results for East St. Louis, the main sources of organic aerosol were found to be mobile sources, secondary organic aerosols (SOAs), resuspended soil and biomass combustions, as well as an n-alkane dominated point source and other combustion sources. The MM-PMF model was reasonably stable when the number of observations in the input was reduced to ninety, or approximately 33% of observations present in the base case. In these cases, the key factors including resuspended soil, mobile and secondary factors, which accounted for more than 70% of the measured OC concentrations, were stable as defined by a relative standard deviation (RSD) of less than 30%. Similar results were obtained from the smaller data subsets, but resulted in larger uncertainties, with several of these factors yielding RSD of greater than 30%. The three factors with the largest OC contributions were more stable than the other minor factors, even when the number of observations was nominally 50 days. Secondary organic aerosol (SOA) was the most stable factor observed in the model runs. Since it is unclear if these results can be broadly applied to all MM-PMF models, additional studies of this nature are needed to assess the broader applicability of these conclusions. Until such studies are implemented, this paper provides a foundation to design future studies in sampling strategies for source apportionment using MM-PMF. (C) 2009 Elsevier Ltd. All rights reserved.