Adjoint-based computation of U.S. nationwide ozone exposure isopleths

Population exposure to daily maximum ozone is associated with an increased risk of premature mortality, and efforts to mitigate these impacts involve reducing emissions of nitrogen oxides (NOx) and volatile organic compounds (VOCs). We quantify the dependence of U.S. national exposure to annually averaged daily maximum ozone on ambient VOC and NOx concentrations through ozone exposure isopleths, developed using emissions sensitivities from the adjoint of the GEOS-Chem air quality model for 2006. We develop exposure isopleths for all locations within the contiguous US and derive metrics based on the isopleths that quantify the impact of emissions on national ozone exposure. This work is the first to create ozone exposure isopleths using adjoint sensitivities and at a large scale. We find that across the US, 29% of locations experience VOC-limited conditions (where increased NOx emissions lower ozone) during 51% of the year on average. VOC-limited conditions are approximately evenly distributed diurnally and occur more frequently during the fall and winter months (67% of the time) than in the spring and summer (37% of the time). The VOC/NOx ratio of the ridge line on the isopleth diagram (denoting a local maximum in ozone exposure with respect to NOx concentrations) is 9.2 ppbC/ppb on average across grid cells that experience VOC-limited conditions and 7.9, 10.1 and 6.7 ppbC/ppb at the three most populous US cities of New York, Los Angeles and Chicago, respectively. Emissions that are ozone exposure-neutral during VOC-limited exposure conditions result in VOC/NOx concentration ratios of 0.63, 1.61 and 0.72 ppbC/ppb at each of the three US cities respectively, and between 0.01 and 1.91 ppbC/ppb at other locations. The sensitivity of national ozone exposure to NOx and VOC emissions is found to be highest near major cities in the US. Together, this information can be used to assess the effectiveness of NOx and VOC emission reductions on mitigating ozone exposure in the US, determine where they will be counterproductive, and quantify the optimal NOx/VOC reduction ratio.