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An organic tracer method, recently proposed for estimating individual contributions of toluene and α-pinene to secondary organic aerosol (SOA) formation, was evaluated by conducting a laboratory study where a binary hydrocarbon mixture, containing the anthropogenic aromatic hydrocarbon,toluene, and the biogenic monoterpene, α-pinene, was irradiated in air in the presence of NOx to form SOA. The contributions of toluene and α-pinene to the total SOA concentration, calculated using the organic tracer method, were compared with those obtained with a more direct 14C content method. In the study, SOA to SOC ratios of 2.07 ± 0.08 and 1.41 ± 0.04 were measured for toluene and α-pinene SOA, respectively. The individual tracer-based SOA contributions of 156 µg m-3 for toluene and 198 µg m-3 for α-pinene, which together accounted for 82% of the gravimetrically determined total SOA concentration, compared well with the 14C values of 182 and 230 µg m-3 measured for the respective SOA precursors. While there are uncertainties associated with the organic tracer method, largely due to the chemical complexity of SOA forming chemical mechanisms, the results of this study suggest the organic tracer method may serve as a useful tool for determining whether a precursor hydrocarbon is a major SOA contributor. [ABSTRACT FROM AUTHOR]

A laboratory study was carried out to investigate the secondary organic carbon (SOC) yields of α-pinene and isoprene in the presence of SO2, which produces acidic aerosol in the system. Experiments were based on irradiating each hydrocarbon (HC) with NOx in a 14.5 m³ smog chamber operated in the dynamic mode. The experimental design consisted of several multi-part experiments for each HC. In the first part of each experiment, an HC/NOx irradiation was conducted in the absence of SO2 and was followed by irradiations with the addition of SO2 in subsequent parts. Filter-based analyses for organic carbon were made using a thermal-optical approach either with an off-line instrument or in situ with an automated instrument. For isoprene in the absence of SO2, the SOC yield was approximately 0.001, a value consistent with earlier work from this laboratory. With the addition of up to 200 ppb SO2, the yield increased by a factor of 7. For α-pinene in the absence of SO2, the SOC yield of the irradiated mixture was found to average 0.096 from two experiments. With SO2 in the system, the SOC yield increased on average to 0.132. These results suggest that SO2, and by inference acidic aerosol, may play a role in increasing the yield of SOC from the photooxidation products of biogenic hydrocarbons or by the direct uptake of biogenic hydrocarbons onto acidic aerosol. [ABSTRACT FROM AUTHOR]

Atmospheric standards containing parts-per-billion levels of 14 semivolatile hydrocarbon compounds, including eight sesquiterpenes (SQTs) (longipinene, α-copaene, isolongifolene, α-cedrene, trans-caryophyllene, aromadendrene, α-humulene,δ-cadinene), two oxidized sesquiterpenoids (cis-nerolidol, trans-nerolidol), one biogenic ketone (geranyl-acetone) and three aromatic compounds (1,3,5-tri-isopropylbenzene, diphenylmethane, nonylbenzene), were collected onto four solid adsorbent materials at increasing ozone mixing ratios (0-100 ppbv O3) for analysis by thermodesorption-gas chromatography. Substantial sampling losses of up to >90% were found for the most reactive SQT, even at the lowest ozone level investigated of 20 ppbv. Loss rates from the ozone–SQT reaction were used to derive estimates of gas-phase ozone reaction rate constants for longipinene, α-copaene, isolongifolene, geranylacetone, aromadendrene, δ-cadinene, cis-nerolidol, and trans-nerolidol. Three different ozone mitigation techniques were investigated to prevent these sampling losses. These strategies included (a) placing glass fiber filters impregnated with sodium thiosulfate (Na2S2O3) into the sampling line, (b) titration of ozone in the sampling stream with nitric oxide (NO), and (c) catalytically removing ozone with a commercially available manganese dioxide (MnO2) catalyst. All three techniques reduced ozone-mixing ratios from 100 ppbv to <0.6 ppbv at sampling flow rates of 1 L min-1. When the Na2S2O3 fitters and the NO-titration techniques were applied, SQT loss rates decreased from 25-60% to 0-5% for most SQT compounds and from >90% to ∼-10-50% for the two most reactive compounds at ozone mixing ratios of up to 100 ppbv. The commercial manganese dioxide scrubber, however, caused complete analyte losses (>98%) even at 0 ppbv ozone. These results underline the need and present applicable techniques for removal of ozone in air samples for SQT analysis by solid adsorption techniques. [ABSTRACT FROM AUTHOR]