Estimation of secondary organic aerosol formation from semi-continuous OC–EC measurements in a Madrid suburban area

Abstract

An analysis of hourly measurements of gaseous pollutants and fine carbonaceous aerosol (PM 2.5) divided into two fractions, elemental and organic carbon (EC and OC), in a suburban Madrid metropolitan area site is presented. Data were obtained using a semi-continuous thermal analyser for two periods of time during the summer and late autumn–early winter of 2003. In the summer period, correlation between EC and OC was poor ( r = 0.4 6 ), and high OC/EC ratios were usually found. In contrast, during the late autumn–early winter period the two carbonaceous aerosol fractions showed a high degree of correlation ( r = 0.9 4 ). Coincident peaks of OC and secondary gases (NO 2+O 3) were observed during summer episodes and also on some winter episodic days, suggesting a significant non-primary contribution to OC in fine aerosol, linked to photochemical oxidation of gaseous pollutants. OC apportionment between primary and secondary origins has been attempted for the two measuring periods using the EC tracer model. In the summer period, the results of this apportionment were very dependent on the y-intercept value (considered as the non-combustion OC background concentration) of selected linear regressions. Calculation of the secondary contribution to the OC fraction during polluted days gave diurnal maximum hourly estimations in a range from 35% to 55% and daily estimations averaged during the 10–19 h period ranging from 25% to 45%. Thus, this would confirm a daily urban photochemical origin for the secondary organic aerosol, although biogenic contribution to both the OC background and the SOA formation may be significant in the area during summer. During late autumn–early winter episodes primary contribution to OC was more prevailing, although the model also estimated maximum hourly values of secondary OC in the order of 35% of the measured OC.