Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions.

The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.

Identification of organic hydroperoxides and hydroperoxy acids in secondary organic aerosol formed during the ozonolysis of different monoterpenes and sesquiterpenes by on-line analysis using atmospheric pressure chemical ionization ion trap mass spectrometry.

On-line ion trap mass spectrometry (ITMS) enables the real-time characterization of reaction products of secondary organic aerosol (SOA). The analysis was conducted by directly introducing the aerosol particles into the ion source. Positive-ion chemical ionization at atmospheric pressure (APCI(+)) ITMS was used for the characterization of constituents of biogenic SOA produced in reaction-chamber experiments. APCI in the positive-ion mode usually enables the detection of [M+H](+) ions of the individual SOA components. In this paper the identification of organic peroxides from biogenic volatile organic compounds (VOCs) by on-line APCI-ITMS is presented. Organic peroxides containing a hydroperoxy group, generated by gas-phase ozonolysis of monoterpenes (alpha-pinene and beta-pinene) and sesquiterpenes (alpha-cedrene and alpha-copaene), could be detected via on-line APCI(+)-MS/MS experiments. A characteristic neutral loss of 34 Da (hydrogen peroxide, H(2)O(2)) in the on-line MS/MS spectra is a clear indication for the existence of an organic peroxide, containing a hydroperoxy functional group.

Characterization of oligomeric compounds in secondary organic aerosol using liquid chromatography coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

The components of secondary organic aerosols (SOAs) generated from the gas-phase ozonolysis of two C(10)H(16)-terpenes (alpha-pinene; sabinene) and a cyclic C(6)H(10) alkene (cyclohexene) were characterized by the use of a Fourier transform ion cyclotron mass spectrometer equipped with an electrospray ionization source operated in the negative ion mode. Reversed-phase high-performance liquid chromatography was used to achieve chromatographic separation of highly oxidized organic compounds. In addition to the well-known group of low molecular weight oxidation products (monomers; e.g. dicarboxylic acids), higher molecular weight compounds (dimers) were also detected and their exact elemental compositions were determined. In order to provide additional information for the structural elucidation of these compounds, collision-induced dissociation was applied. Based on the MS/MS spectra, two higher molecular weight products are proposed to be an ester and a peroxide. Molecular formulae calculated from the exact masses show that the SOA-compounds are heavily oxidized and this information creates the background to a discussion of potential reaction pathways for the formation of higher molecular weight compounds.

Characterization of selected organic compound classes in secondary organic aerosol from biogenic VOCs by HPLC/MSn.

The formation of secondary organic aerosols (SOA) has been investigated intensively during the last two decades in numerous field and laboratory studies and a general understanding exists about the major particle-phase products. However, recent studies show that several new product classes, such as esters, peroxides or organosulfates, also have to be considered in order to understand the detailed chemical mechanisms leading to SOA as well as to predict the aerosol mass loadings. For the identification and quantification of these three compound classes as well as for carboxylic SOA compounds, liquid chromatography (LC)/mass spectrometry (MS) is the most appropriate analytical method. In this article we try to summarize briefly the work that has been done for the determination of SOA-related carboxylic acids and we present new LC/tandem MS results on the characterization of esters, peroxides and organosulfates. In contrast to earlier work, the mass-spectrometric characterization of the individual compounds is always based on the comparison with authentic reference compounds.