The Effect of Solvent on the Analysis of Secondary Organic Aerosol Using Electrospray Ionization Mass Spectrometry
Journal Article
·
· Environmental Science and Technology
- Univ. of California, Irvine, CA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Solvent-analyte reactions in organic aerosol (OA) extracts prepared for analysis by electrospray ionization mass spectrometry (ESI-MS) were examined. Secondary organic aerosol (SOA) produced by ozonation of d-limonene as well as several test organic chemicals with functional groups typical for OA constituents were dissolved and stored in methanol, d3-methanol, acetonitrile, and d3-acetonitrile to investigate the extent and relative rates of reactions between analyte and solvent. High resolution ESI-MS showed that reactions of carbonyls with methanol produce significant amounts of hemiacetals and acetals on time scales ranging from several minutes to several days, with the reaction rates increasing in acidified solutions. Carboxylic acid groups were observed to react with methanol resulting in the formation of esters. In contrast, acetonitrile extracts showed no evidence of reactions with analyte molecules, suggesting that acetonitrile is the preferred solvent for SOA extraction. The use of solvent-analyte reactivity as an analytical chemistry tool for the improved characterization of functional groups in complex organic mixtures was also demonstrated. Direct comparison between ESI mass spectra of the same SOA samples extracted in reactive (methanol) versus non-reactive (acetonitrile) solvents was used to estimate the relative fractions of ketones (≥38%), aldehydes (≥6%), and carboxylic acids (≥55%) in d-limonene SOA.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States), Environmental Molecular Sciences Laboratory (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 946623
- Report Number(s):
- PNNL-SA--59973; 24392; 25638; KC0302020
- Journal Information:
- Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 19 Vol. 42; ISSN 0013-936X
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
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