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Abstract

Mercury is a global pollutant and neurotoxin that bioaccumulates within food chains and can cause adverse health effects with exposure. Although elemental mercury can persist in the atmosphere for months, it can also undergo oxidation chemistry to a more water soluble form that is readily removed from the atmosphere and introduced into ecosystems. However, the chemical mechanisms for mercury oxidation are not well understood. During the spring and summer seasons of 2021 and 2022, continuous measurements of oxidized and elemental mercury, meteorology, trace gases, and aerosol properties were collected at the high elevation Storm Peak Laboratory in Steamboat Springs, Colorado to investigate the origins of atmospheric oxidized mercury and the conditions under which oxidation occurs in a continental environment. We examined this dataset for multi-day periods in which oxidized mercury was at least one standard deviation above the seasonal mean for spring and summer. We generated descriptive statistics and correlation coefficients of meteorological and chemical tracers to examine these multi-day events for air mass composition. We also ran HYSPLIT 10-day back trajectories every six hours using GDAS input meteorological data at 1000 m AGL to examine air mass origins. We then categorized the events based on similarities in composition and transport into three types: Clean Air Events, Elevated Ozone Events, and Combustion Tracer Influenced Events. During the identified episodes, hourly-averaged oxidized mercury concentrations ranged from 121 ± 25 pg/m3 to 198 ± 26 pg/m3. Across most events, oxidized mercury was significantly anticorrelated with elemental mercury and relative humidity, and relative humidity remained below 40%, suggesting the occurrence of in-situ oxidation in dry air masses potentially of free tropospheric origin. These results validate and expand upon earlier work at SPL and will be used to further study the underlying chemistry for atmospheric mercury oxidation.

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