Title: Variability in Tropospheric Oxidation from Polluted to Remote Regions
Description: Tropospheric oxidation modulates pollution chemistry and greenhouse gas lifetimes. The hydroxyl radical (OH) is the primary oxidant and the main sink for methane, the second-most influential anthropogenic contributor to climate change. OH is produced following the photolysis of ozone, an oxidant, respiratory irritant and greenhouse gas. Trends in methane or ozone are frequently attributed to their sources, but sink-driven variability is less often considered. I investigate the influence of fluctuations in turbulent loss to the Earth’s surface, also known as deposition, on tropospheric ozone concentrations and chemistry over the relatively polluted eastern United States. I use idealized sensitivity simulations with the global chemistry-climate model AM3 to demonstrate that coherent shifts in deposition, on the order recently observed at a long-term measurement site, affect surface ozone concentrations as much as decreases in its precursor emissions have over the past decade. I conclude that a sub-regional deposition measurement network is needed to confidently attribute trends in tropospheric ozone.

Next, I turn to the remote marine troposphere to evaluate two theoretical proxies for variability in the methane sink, OH, with observations from the NASA Atmospheric Tomography (ATom) aircraft campaign. The low concentration and short lifetime of OH preclude the development of a representative measurement network to track its fluctuations in space and time. This dearth of constraints has led to discrepancies in the methane lifetime across models that project atmospheric composition and climate. Observational and modeling studies suggest that few processes control OH fluctuations in relatively clean air masses, and the short OH lifetime implies that it is at steady-state (total production is equal to loss). I leverage this chemistry by evaluating a convolution of OH drivers, OH production scaled by the lifetime of OH against its sink with carbon monoxide, as a potential “steady-state” proxy. I also assess the predictive skill of formaldehyde (HCHO), an intermediate product of the methane and OH reaction.

I find that both proxies broadly reflect OH on sub-hemispheric scales (2 km altitude by 20° zonal bins) relative to existing, well-mixed proxies that capture, at best, hemispheric OH variability. HCHO is produced following methane loss by reaction with OH and reflects the insolation influence on OH, while the steady-state proxy demonstrates a stronger relationship with OH and offers insight into its sensitivity to a wider array of drivers. Few components—water vapor, nitric oxide, and the photolysis rate of ozone to singlet-d atomic oxygen—dominate steady-state proxy variance in most regions of the remote troposphere, with water vapor controlling the largest spatial extent. Current satellite instruments measure water vapor directly, and other retrievals like nitrogen dioxide columns or aerosol optical depth or could be used to infer nitric acid or the rate of ozone photolysis. Thus satellite observations may be used to derive a steady-state proxy product to infer OH variability and sensitivity in the near-term.

HCHO is also retrieved from satellite instruments, and an OH product using satellite-observed HCHO columns is already in development. The relatively high fluctuation frequency of HCHO or the steady-state proxy advances our insight into the connection between OH and its drivers. The observed steady-state proxy demonstrates a widespread sensitivity to water vapor along the ATom flight tracks, and I conclude that an improved and consistent representation of the water vapor distribution is a necessary step in constraining the methane lifetime across global chemistry-climate models.