Identification of Transportation Contributions to Urban PM Levels AQRB Mid-Term Review 2004 J.R. Brook + many contributors MSC

Overview PERD 'POL' on transportation and particulate matter. –Multiple Gov't partners –Emphasis on organic fraction Continuing analysis of Toronto and Vancouver 'TSRI' daily time series of PM 2.5 speciation. –Receptor modelling Organic speciation of PM 2.5

Measurement of OC & EC Thermal-Optical Transmission Analysis (TOT)

OC & EC Measurement Uncertainties High OC blanks (7-15  g per filter) Deposit non-uniformity (~10% variability) Uncertainty in pyrolysis correction based upon BC absorbance (laser) SVOC –Positive and negative artifacts Enhanced charring due to artifacts and blank OC EC biased low? Conversion from ‘OC’ to ‘OM’

Toronto Vancouver Oxalic (  g m -3 ) Other acids (  g m -3 ) Malonic Malic Succinic Azelaic Oxalic CWWC NO (x100 ppb) EC (  gC m -3 ) O 3 (x10ppb) OC1-3 OC4 (  gC m -3 ) OC1-3 OC4 O3O3 BC NO CWWC Time series of LMW acids & OC1-3, OC4, BC, NO and O 3

PMF Estimates of PM 2.5 Sources - Toronto Coal Combustion Ammonium Nitrate Motor Vehicles

Sources of Organic Carbon - PMF PM primary-2 smelter PM primary-1 LMW acid Road salt/vehicle Vehicle/road dust Amm. Nitrate Sec. Coal

Comparison of 2 Multi-Variate Methods 1.9% 2.2% 0.6% 3.7% 13.1% 8.0% 36.2% 18.2% 16.1% 2.2% 1.4% 8.2% 10.1% 14.4% 1.3% 36.5% 26.0% PMF UNMIX

Temporal Variation in PMF Sources For the 3 UNMIX motor vehicle related sources, day-of-week pattern is strongest for Diesel, weakest for Gas & intermediate for Road Dust. Day of week means are similar between the 2 PMF and 3 UNMIX motor vehicle related sources.

Vancouver PMF Source Characteristics

PMF Estimate of PM 2.5 Sources - Vancouver % Contribution to PM 2.5

OC1-3 (  gC m -3 ) MV-PMF (  g m -3 ) SOA-PMF (  g m -3 ) Vancouver Toronto Relationship between OC and its two important sources

GOATS Concentrations Concentrations are in ng m -3 unless noted PM 2.5 “semi-hivol” sampling in spring-summer 2000 Yonge – eastbound 401 on ramp from northbound Yonge St. Downsview – roof of MSC Egbert – Centre for Atmospheric Research Experiments

GOATS %OC Explained Concentration (ng m -3 ) 13%28%28%15%39%32%9%6% Humic-like substances (‘HULIS’) is one of the more exciting areas of OC-speciation research at present time. *OC4 and the ‘UCM or hump’ are hypothesized to be related to HULIS *polymerized carbonyl compounds could be part of HULIS Importance of primary biologicals is also becoming increasingly recognized. *4-11% of PM 2.5 at Yonge was found to be associated with fungal spores.

Future Activities Renewal of PERD-POL is pending CRUISER has been proposed to take a central role in the ambient characterization component of this new POL A new joint proposal on black carbon and climate effects has been submitted to the Climate Change Technology & Innovation Transportation R&D program Ongoing comparison of independent receptor model results using same data and similar and different methods (MSC, UofT, P&Y) Past organic speciation results continue to be analyzed Progress is slow due to lack of time Two years of monthly average concentrations (a composite of daily samples from downtown Toronto TSRI site) of a range of organic species is nearing completion. Analysis of levoglucosan, fatty acids, alkanes and biomarkers to begin soon Will provide our first look at the seasonal cycle in Toronto Methods are being developed for TD-CGMS No solvents or extraction Can utilize low volume samples First step is to focus on PAHs and alkanes for health/exposure studies

Sources of Selected Constituents UNMIX Model