Particulate matter and manganese exposures in Toronto,Canada

Methylcyclopentadienyl manganese tricarbonyl (MMT) is a manganese-based gasoline additive used to enhance automobile performance. MMT has been used in Canadian gasoline for about 20 yr. Because of the potential for increased levels of Mn in particulate matter resulting from automotive exhausts, a large-scale population-based exposure study (～1000 participant periods) was conducted in Toronto, Canada, to estimate the distribution of 3-day average personal exposures to particulate matter (PM_2.5 and PM₁₀) and Mn. A stratified, three-stage, two-phase probability, longitudinal sample design of the metropolitan population was employed. Residential indoor and outdoor, and ambient levels (at a fixed site and on a roof) of PM_2.5, PM₁₀, and Mn were also measured. Supplementary data on traffic counts, meteorology, MMT levels in gasoline, personal occupations, and activities (e.g. amount of vehicular usage) were collected. Overall precision (%RSD) for analysis of duplicate co-located samples ranged from 2.5 to 5.0% for particulate matter and 3.1 to 5.5% for Mn. The detection limits were 1.47 and 3.45 μg m^-3 for the PM₁₀ and PM_2.5 fractions, respectively, and 5.50 and 1.83 ng m^-3 for Mn in PM₁₀ and PM_2.5, respectively. These low detection limits permitted the reporting of concentrations for >98% of the samples. For PM₁₀, the personal particulate matter levels (median 48.5 μg m^-3) were much higher than either indoor (23.1 μg m^-3) or outdoor levels (23.6 μg m^-3). The median levels for PM_2.5 for personal, indoor, and outdoor were 28.4, 15.4 and 13.2 μg m^-3, respectively. The correlation between PM_2.5 personal exposures and indoor concentrations was high (0.79), while correlations between personal and the outdoor, fixed site and roof site were low (0.16–0.27). Indoor Mn concentration distributions (in PM_2.5 and PM₁₀), unlike particulate matter, exhibited much lower and less variable levels that the corresponding outdoor data. The median personal exposure was 8.0 ng m^-3, compared with 4.7 and 8.6 ng m^-3, respectively, for the indoor and outdoor distributions. The highest correlations occurred for personal vs indoor data (0.56) and for outdoor vs roof site data (0.66), and vs fixed site data (0.56). The concentration of Mn in particulate matter, expressed in ppm (w/w), revealed that the fixed site was the highest, followed by the roof site, outdoor, indoor, and personal. The personal and indoor data showed a statistically significant correlation (0.68) while all other correlations between personal or indoor data and outdoor or fixed-site data were quite small. The low correlations of personal and indoor levels with outdoor levels suggest that different sources in the indoor and outdoor microenvironments produce particle matter with dissimilar composition. The correlation results indicate that neither the roof- nor fixed-site concentrations can adequately predict personal particulate matter or Mn exposures.