Determination of Organic Compounds Present in Airborne Particulate Matter

Abstract

Fine organic aerosol samples (d_p ≤ 2.1 µm) were collected systematically during the entire year 1982 at four urban sites in the greater Los Angeles area and at one remote station: West Los Angeles, Downtown Los Angeles, Pasadena, Rubidoux, and San Nicolas Island. Samples were taken at 6-day intervals and composited to form monthly sample sets. The aerosol sample composites were subjected to high resolution gas chromatography (HRGC) and gas chromatography/rnass spectrometry (GC/MS). The objective is to quantify the abundance and seasonal variation of individual organic compounds that may be diagnostic for the contribution of particular emission sources to the ambient organic complex. More than 80 organic compounds are quantified, including the series of a-alkanes, g-alkanoic acids, n-alkenoic acids, n-alkanals, and aliphatic dicarboxylic acids, as well as aromatic polycarboxylic acids, diterpenoids, polycyclic aromatic hydrocarbons, polycyclic aromatic ketones and quinones, nitrogen-containing organic compounds, and other organics. Primary organic aerosol constituents are readily identified, revealing an annual pattern with high winter concentrations and low summer concentrations in the Los Angeles area. In contrast, dicarboxylic acids of likely secondary origin show a reverse pattern, with high concentration in late spring/early summer. The total ambient annual average dicarboxylic acids concentration shows a steady increase when moving in the prevailing summer downwind direction from the most western urban sampling site (West Los Angeles) to the farthest eastern sampling location (Rubidoux), with an increase from 199 ng m^(-3) at West Los Angeles to 312 ng m^(-3) at Rubidoux. The occurrence of aromatic polycarboxylic acids in the fine particulate matter is discussed in detail in this study, including possible sources and formation pathways. The total aromatic polycarboxylic acid concentration reveals elevated summer concentrations when compared to the annual concentration cycle, indicating increased formation or/and emissions in summertime. Polycyclic aromatic hydrocarbons (PAH's), without exception, show low summer and high winter concentrations; whereas, polycyclic aromatic ketones (PAK's) and quinones (PAQ's) show slightly increased input/formation during early summer, indicating possible atmospheric chemical reactions involving PAH's as precursor compounds. Molecular markers characteristic of wood smoke are identified, and their concentrations change by season in close agreement with prior estimates of the seasonal use of wood as a fuel. The total mass concentration of identified aerosol organic compounds ranges from about 650 ng m^(-3) (West LA) to about 760 ng m^(-3) (Downtown LA) on an annual basis. Subdividing the total identified masses into their single compound classes reveals that n-alkanoic acids and aliphatic dicarboxylic acids make up the main portions quantified, followed by aromatic polycarboxylic acids, n-alkanes, diterpenoid acids, and polycyclic aromatic hydrocarbons. This compilation of fine organic aerosol data on a molecular level provides an extensive catalog of the organic compounds quantified, covering an entire year. Further research is underway to characterize the organic aerosol released by primary emission sources in the Los Angeles area. That study will not only provide complete characterizations of these emissions sources on a molecular basis, but in addition will enable the identification and quantification of additional organic compounds in the same airborne particle samples which otherwise would have gone unidentified in the complexity of the organic matrix inherent in fine airborne particle samples. In the future, these data from the monitoring network can be used to evaluate the predictions of mathematical models for the atmospheric transport and reaction of organic aerosol constituents defined at a molecular level.