Spectrophotometric methods developed previously to quantify the major functional groups present in oxidized organic aerosol were modified for use with sample masses typical of those collected from ambient air. In these methods, carbonyl, hydroxyl, carboxyl, and ester groups are reacted with derivatizing agents that are specific to each functional group to form strongly light absorbing derivatives, a colored peroxide solution is formed through redox chemistry, and nitrates have an inherently strong absorbance. As described here, improved detection limits are made possible by measuring absorbance using a spectrophotometer that requires only a few microliters of solution for analysis, instead of the five milliliter volume required previously when using a standard cuvette. Use of this so-called NanoPhotometer allows comparable absorbances to be obtained with much less mass by concentrating samples by more than two orders of magnitude relative to previous methods. Detection limits are approximately 0.03, 0.02, 0.3, 1, 1, and 0.07 nmoles for carbonyl, hydroxyl, carboxyl, ester, peroxide, and nitrate groups, which correspond to approximately 0.8, 0.6, 10, 40, 50, and 5 ng of each functional group. In practice, depending on the composition of functional groups, the mass required for complete analysis of moderately oxidized organic aerosol is »10-100 mg. The new microscale methods were shown to provide good linearity, precision, and accuracy by comparing results from the analysis of standards and aerosol formed from reaction of a-pinene and O 3 with results obtained using the previously developed macroscale methods. The evaluation demonstrates that the microscale methods can be used to quantify these six functional groups at low organic aerosol mass concentrations.

Previous studies have shown that 1,4-hydroxycarbonyls, which are often major products of the atmospheric oxidation of hydrocarbons, can undergo acid-catalyzed cyclization and dehydration in aerosol particles to form highly reactive unsaturated dihydrofurans. In this study the kinetics of dehydration of cyclic hemiacetals, the rate-limiting step in this process, was investigated in a series of environmental chamber experiments in which secondary organic aerosol (SOA) containing cyclic hemiacetals was formed from the reaction of n-pentadecane with OH radicals in dry air in the presence of HNO3. A particle beam mass spectrometer was used to monitor the formation and dehydration of cyclic hemiacetals in real time, and SOA and HNO3 were quantified in filter samples by gravimetric analysis and ion chromatography. Measured dehydration rate constants increased linearly with increasing concentration of HNO3 in the gas phase and in SOA, corresponding to catalytic rate constants of 0.27 h(-1) ppmv(-1) and 7.0 h(-1) M(-1), respectively. The measured Henry's law constant for partitioning of HNO3 into SOA was 3.7 × 10(4) M atm(-1), ∼25% of the value for dissolution into water, and the acid dissociation constant was estimated to be <8 × 10(-4), at least a factor of 10(4) less than that for HNO3 in water. The results indicate that HNO3 was only weakly dissociated in the SOA and that dehydration of cyclic hemiacetals was catalyzed by molecular HNO3 rather than by H(+). The Henry's law constant and kinetics relationships measured here can be used to improve mechanisms and models of SOA formation from the oxidation of hydrocarbons in dry air in the presence of NOx, which are conditions commonly used in laboratory studies. The fate of cyclic hemiacetals in the atmosphere, where the effects of higher relative humidity, organic/aqueous phase separation, and acid catalysis by molecular H2SO4 and/or H(+) are likely to be important, is discussed.

A systematic approach for identifying and quantifying molecular components of complex organic aerosol mixtures is presented. The approach combines methods developed previously for derivatizing carbonyl, hydroxyl, carboxyl, and ester functional groups, which are commonly present in oxidized organic aerosol, with liquid chromatography, UV detection, and chemical ionization-ion trap mass spectrometry. The original derivatization-spectrophotometric methods were modified for compatibility with liquid chromatography and then evaluated by analyzing a variety of standard compounds that contain one or more functional groups. Detection limits for carbonyl, hydroxyl, carboxyl, and ester analysis are approximately 0.003, 0.02, 0.01, and 1 nmole, respectively. Mass spectral analysis of derivatives using isobutane and ammonia as reagent gases for chemical ionization can be used to determine compound molecular weight, and characteristic fragmentation patterns provide structural information for use in compound identification. The methods will be useful for analyzing the chemical composition of secondary organic aerosol (SOA) formed in laboratory studies to obtain information needed to develop quantitative reaction mechanisms that can be incorporated into atmospheric models to better predict the formation, composition, and fate of SOA.