Photochemical Conversion of Surrogate Emissions for Use in Toxicological Studies: Role of Particulate- and Gas-Phase Products.

The production of photochemical atmospheres under controlled conditions in an irradiation chamber permits the manipulation of parameters that influence the resulting air-pollutant chemistry and potential biological effects. To date, no studies have examined how contrasting atmospheres with a similar Air Quality Health Index (AQHI), but with differing ratios of criteria air pollutants, might differentially affect health end points. Here, we produced two atmospheres with similar AQHIs based on the final concentrations of ozone, nitrogen dioxide, and particulate matter (PM2.5). One simulated atmosphere (SA-PM) generated from irradiation of ∼23 ppmC gasoline, 5 ppmC α-pinene, 529 ppb NO, and 3 µg m-3 (NH4)2SO4 as a seed resulted in an average of 976 µg m-3 PM2.5, 326 ppb NO2, and 141 ppb O3 (AQHI 97.7). The other atmosphere (SA-O3) generated from 8 ppmC gasoline, 5 ppmC isoprene, 874 ppb NO, and 2 µg m-3 (NH4)2SO4 resulted in an average of 55 µg m-3 PM2.5, 643 ppb NO2, and 430 ppb O3 (AQHI of 99.8). Chemical speciation by gas chromatography showed that photo-oxidation degraded the organic precursors and promoted the de novo formation of secondary reaction products such as formaldehyde and acrolein. Further work in accompanying papers describe toxicological outcomes from the two distinct photochemical atmospheres.

Combustion-Related Organic Species in Temporally Resolved Urban Airborne Particulate Matter.

Accurate characterization of the chemical composition of particulate matter (PM) is essential for improved understanding of source attribution and resultant health impacts. To explore this we conducted ambient monitoring of a suite of 15 combustion-related organic species in temporally resolved PM 2.5 samples during an ongoing animal exposure study in a near source environment in Detroit, MI. All of the 15 species detected were above the method detection limit in 8 hour samples. This study focused on two molecular classes: Polycyclic Aromatic Hydrocarbons (PAHs) and Hopanes measured in samples. Of the 12 PAHs studied, benzo[b]fluoranthene (169 pg m-3), benzo[g,h,i]perylene (124 pg m-3), and benzo[e]pyrene (118, pg m-3) exhibited the three highest mean concentrations while 17α(H),21ß(H)-Hopane (189 pg m-3) and 17α(H),21ß(H)-30-Norhopane (145 pg m-3) had the highest mean concentrations of the 3 Hopanes analyzed in samples. Ratios of individual compound concentrations to total compound concentrations (∑ 15 compounds) showed the greatest daily variation for 17α(H),21ß(H)-Hopane (11-28%) and 17α(H),21ß(H)-30-Norhopane (8-20%). Diagnostic PAH concentration ratios ([IP]/[IP + BP] (range 0.30 - 0.45), [BaP]/[BaP+BeP] (range 0.26 - 0.44), [BaP]/[BP] (range 0.41 - 0.82), [Bb]/[Bk] (range 2.07 - 2.66), in samples reflected impacts froma mixture of combustion sources consistent with greater prevalence of petroleum combustion source emissions (gasoline, diesel, kerosene, and crude oil) compared to coal or wood combustion emissions impacts at this urban site. Results from this study demonstrate that short duration sampling for organic speciation provides temporally relevant exposure information.

Trueness, precision, and detectability for sampling and analysis of organic species in airborne particulate matter.

Recovery, precision, limits of detection and quantitation, blank levels, calibration linearity, and agreement with certified reference materials were determined for two classes of organic components of airborne particulate matter, polycyclic aromatic hydrocarbons and hopanes, using typical sampling and gas chromatography/mass spectrometry analysis methods. These determinations were based on initial method proficiency tests and on-going internal quality control procedures. Recoveries generally ranged from 75% to 85% for all target analytes and collocated sample precision estimates were generally better than 20% for polycyclic aromatic hydrocarbons and better than 25% for hopanes. Results indicated substantial differences in data quality between the polycyclic aromatic hydrocarbons and hopanes. Polycyclic aromatic hydrocarbons demonstrated better collocated precision, lower method detection limits, lower blank levels, and better agreement with certified reference materials than the hopanes. The most serious area of concern was the disagreement between measured and expected values in the standard reference material for hopanes. With this exception, good data quality was demonstrated for all target analytes on all other data quality indicators.