Observations of Vertical Gradients in Composition, Oxidation States, and Diurnal Dynamics for a Comprehensive Suite of VOCs from 10 to 525 m in the San Joaquin Valley, California

Abstract:

Volatile organic compounds (VOCs) are emitted by numerous anthropogenic and biogenic sources and undergo oxidative processing, as well as horizontal and vertical transport, in the troposphere. Understanding the dynamics of chemical and physical land atmosphere exchange processes and their impacts on atmospheric chemistry requires high temporal resolution of observations at multiple heights and the knowledge of the sources and sinks.

We measured dynamic composition changes of VOCs as a function of height (5 inlets from 10 to 525 m, switching every 2 minutes, full profile every 10 minutes) for more than a year using a PTR-QMS. Here, we focus on a multi-week period in February 2013 when simultaneous SRI-TOFMS and PTR-QMS took place.

More than 300 ions were detected within an m/z range of 0.000 – 400.000 Th and 260 ions were analyzed. Chemical formulas were assigned to more than 50% of these ions. Late winter is a period when anthropogenic influences are relatively high including remote sources in the Central Valley. Biogenic influences are low at this time of year, but were clearly observed. The average diurnal vertical gradients (Figure 1) showed trends and patterns and behavior consistent with boundary layer dynamics, wind profiles and source activity for a broad array of VOCs and source categories. Mass concentration of oxygenated VOCs with 2, 3 or more oxygens or with nitrogen+oxygen had an increasing tendency with height. The opposite was true for pure hydrocarbons and reduced nitrogen containing VOCs which generally decrease with height. The remaining species comprised halogenated as well as other volatile products. Average oxidation state ranged from -2.0 to 4.3.

These observations are useful to reflect the dynamics of VOCs at a rural site in the Central Valley and could be particularly useful for comparison with models of atmospheric chemistry that include PBL dynamics.

Figure 1: Gradient concentration diurnal profiles for 48 selected ions, showing the complexity of VOC dynamics. The color maps represent concentration (ppb). The data shown cover the period of February 12 to February 20, 2013.