Identification of decadal trends and associated causes for organic and elemental carbon in PM2.5 at Canadian urban sites

[Display omitted] •Decadal trends of OC and EC were explored using the advanced time–frequency method.•Significant decrease in EC was mainly caused by reduced on-road emissions.•Slightly decrease in OC was due to two contrasting factors.•OC/EC ratio increased from 2003 to 2019 across Canada. Chemically resolved data for fine particulate matter (PM2.5) have been collected across Canada since 2003 through the National Air Pollution Surveillance (NAPS) network. Seven urban sites that have 10–17 years (2003–2019) of PM2.5 organic carbon (OC) and elemental carbon (EC) data were selected for analysis of decadal trends of OC, EC, and OC/EC ratio using the Ensemble Empirical Mode Decomposition method. Results showed that OC and EC decreased by 0.009–0.072 μg m−3 yr−1 and 0.028–0.049 μg m−3 yr−1, or 0.77–3.1 % yr−1 and 3.2–6.7 % yr−1, respectively, depending on the location. The more rapid decrease in EC than OC resulted in an increasing trend in the OC/EC ratio of 0.03–0.19 yr−1 across the sites. Macro-tracer approach was used to estimate source attributions of OC and EC from wood burning, fossil fuel combustion, and secondary aerosol formation. Using this approach, it was identified that the significant decrease in EC during the past decade was predominately caused by reduced on-road emissions. The decreased emissions from wood burning and transportation dominated the decline of OC, but such a decline was largely offset by the enhanced secondary organic aerosol (SOA) formation, resulting in much weaker decline of OC than EC. The enhanced SOA formation was due to the increased biogenic emissions fully offsetting the decreased anthropogenic emissions for volatile organic compounds. These findings highlight the need for quantifying biogenic sources of VOCs and other oxidants that are involved in OC formation at the national scale.