Exploring the roles of temperature and NOx on ozone production in the Sacramento urban plume

We investigate the role of temperature and NOx (NOx = NO+NO2) on ozone (O3) production in the Sacramento urban plume over a stretch of seven years (2001-2007) using data collected at UC Blodgett Forest Research Station (a forested site in the Sierra Nevadas about 80 km downwind of Sacramento, CA) and at a series of California Air Resources Board (CARB) sites along the Sacramento-Blodgett transect. The consistent daytime wind patterns between the Central Valley of California and the foothills of the Sierra Nevada mountains permits the assumption of plume transport from downtown Sacramento, over the CARB monitoring sites in the eastern suburbs, and past the Blodgett Forest research site. While NOx emissions are limited primarily to the urban and suburban regions of the transect, biogenic volatile organic compound (VOC) emissions are significant throughout the transect, thus there is a fast transition from VOC-limited to NOx-limited as the plume travels away from the urban center, and we have the opportunity to analyze the differences in ozone production across these two chemical regimes. For this analysis, the Sacramento-Blodgett transect is separated into three segments: urban, suburban, and rural, defined by the locations of selected monitoring sites. Ozone concentrations across each segment are controlled by chemical production (Pchem) and loss (Lchem), deposition to surfaces (Ldep), and mixing with background air (Lmix). At an assumed deposition rate, mixing rate, and background O3 concentration, the net chemical flux of ozone (Pchem - Lchem) can be inferred from differences in ozone concentrations between adjacent monitoring sites. We show that ozone production rates, in general, increase with temperature. We also show that decreases in NOx emissions over the period from 2001-2007 have been effective at reducing ozone production at all points along the transect, but only on days where temperatures are highest. At low temperatures, this decrease is less apparent, and in the urban transect, ozone production is observed to increase as NOx concentrations decrease. This is attributed to the high NOx/VOC ratio that results from reduced biogenic emissions and strong local inputs of NOx, thus driving the chemical environment into a NOx-saturated regime. From these results, we give predictions of future ozone exceedences for various emissions and climate scenarios.