Volatile organic compounds and ozone at four national parks in the southwestern United States

The National Park Service is tasked with protecting the lands it oversees, including from impacts from air pollutants. While ozone is regularly monitored in many parks across the United States, precursors to ozone formation are not routinely measured. In this work we characterize volatile organic compounds (VOCs) at four national parks in the southwestern United States: Carlsbad Caverns (CAVE), Great Basin (GRBA), Grand Canyon (GRCA), and Joshua Tree (JOTR). Whole air samples were collected for VOC analysis for five months (mid-April through mid-September) in 2017. Samples were collected from 3 p.m. to 5 p.m. local time, corresponding approximately to the time of expected peak ozone concentrations, and were analyzed using gas chromatography for a variety of compounds including alkanes, alkenes, aromatics, biogenics, and alkyl nitrates. Among the four parks, the total measured VOC mixing ratio was greatest at CAVE, mostly due to an abundance of light alkanes (on average 94% of all VOCs measured) from oil and gas sources. VOC concentrations at the other three parks were similar to each other and approximately 7-10 times lower than at CAVE. While VOC sources varied across sites, VOC-OH reactivity was dominated by biogenic compounds at all sites except CAVE, which had similar contributions from biogenics and from light alkanes. JOTR had the highest levels of ozone, and the highest concentrations of biogenic VOCs among the parks studied. Back trajectory analysis suggests that the high levels of ozone occurred when air flow came from the west, in the direction of the greater Los Angeles area. The two parks most removed from oil and gas and urban sources, GRBA and GRCA, had the lowest concentrations of total VOCs, and were likely influenced by long range transport of pollutants. To better characterize source influences at the park with the highest VOC concentrations, intensive measurements were conducted in and around CAVE for one week in September 2017. These measurements showed an oil and gas influence throughout the region and indicated that the whole air samples collected over the five-month study did not capture the full range of VOC mixing ratios present at other times of the day.