Abstract. Petroleum and dairy operations are prominent sources of gas-phase organic compounds in California's San Joaquin Valley. Ground site measurements in Bakersfield and aircraft measurements of reactive gas-phase organic compounds were made in this region as part of the CalNex (California Research at the Nexus of Air Quality and Climate Change) project to determine the sources contributing to regional gas-phase organic carbon emissions. Using a combination of near-source and downwind data, we assess the composition and magnitude of emissions from these prominent sources that are relatively understudied compared to motor vehicles We also developed a statistical modeling method with the FLEXPART-WRF transport and meteorological model using ground-based data to assess the spatial distribution of emissions in the San Joaquin Valley. We present evidence for large sources of paraffinic hydrocarbons from petroleum extraction/processing operations and oxygenated compounds from dairy (and other cattle) operations. In addition to the small straight-chain alkanes typically associated with petroleum operations, we observed a wide range of branched and cyclic alkanes that have limited previous in situ measurements or characterization in emissions from petroleum operations. Observed dairy emissions were dominated by ethanol, methanol, and acetic acid, and methane. Dairy operations were responsible for the vast majority of methane emissions in the San Joaquin Valley; observations of methane were well-correlated with non-vehicular ethanol, and multiple assessments of the spatial distribution of emissions in the San Joaquin Valley highlight the dominance of dairy operations for methane emissions. The good agreement of the observed petroleum operations source profile with the measured composition of non-methane hydrocarbons in unrefined natural gas associated with crude oil suggests a fugitive emissions pathway during petroleum extraction, storage, or processing with negligible coincident methane emissions Aircraft observations of emission hotspots from operations at oil wells and dairies are consistent with the statistical source footprint determined via transport modeling and ground-based data. At Bakersfield, petroleum and dairy operations each comprised 22–23% of anthropogenic non-methane organic carbon and were each responsible for ~12% of potential precursors to ozone, but their direct impacts as potential SOA precursors were estimated to be minor. A comparison with the California Air Resources Board emission inventory supports the current relative emission rates of reactive organic gases from these sources in the region.

Petroleum and dairy operations are prominent sources of gas-phase organic compounds in California's San Joaquin Valley. It is essential to understand the emissions and air quality impacts of these relatively understudied sources, especially for oil/gas operations in light of increasing US production. Ground site measurements in Bakersfield and regional aircraft measurements of reactive gas-phase organic compounds and methane were part of the CalNex (California Research at the Nexus of Air Quality and Climate Change) project to determine the sources contributing to regional gas-phase organic carbon emissions. Using a combination of near-source and downwind data, we assess the composition and magnitude of emissions, and provide average source profiles. To examine the spatial distribution of emissions in the San Joaquin Valley, we developed a statistical modeling method using ground-based data and the FLEXPART-WRF transport and meteorological model. We present evidence for large sources of paraffinic hydrocarbons from petroleum operations and oxygenated compounds from dairy (and other cattle) operations. In addition to the small straight-chain alkanes typically associated with petroleum operations, we observed a wide range of branched and cyclic alkanes, most of which have limited previous in situ measurements or characterization in petroleum operation emissions. Observed dairy emissions were dominated by ethanol, methanol, acetic acid, and methane. Dairy operations were responsible for the vast majority of methane emissions in the San Joaquin Valley; observations of methane were well correlated with non-vehicular ethanol, and multiple assessments of the spatial distribution of emissions in the San Joaquin Valley highlight the dominance of dairy operations for methane emissions. The petroleum operations source profile was developed using the composition of non-methane hydrocarbons in unrefined natural gas associated with crude oil. The observed source profile is consistent with fugitive emissions of condensate during storage or processing of associated gas following extraction and methane separation. Aircraft observations of concentration hotspots near oil wells and dairies are consistent with the statistical source footprint determined via our FLEXPART-WRF-based modeling method and ground-based data. We quantitatively compared our observations at Bakersfield to the California Air Resources Board emission inventory and find consistency for relative emission rates of reactive organic gases between the aforementioned sources and motor vehicles in the region. We estimate that petroleum and dairy operations each comprised 22% of anthropogenic non-methane organic carbon at Bakersfield and were each responsible for 8-13% of potential precursors to ozone. Yet, their direct impacts as potential secondary organic aerosol (SOA) precursors were estimated to be minor for the source profiles observed in the San Joaquin Valley.

The San Joaquin Valley (SJV) experiences some of the worst ozone air quality in the US, frequently exceeding the California 8 h standard of 70.4 ppb. To improve our understanding of trends in the number of ozone violations in the SJV, we analyze observed relationships between organic reactivity, nitrogen oxides (NOx), and daily maximum temperature in the southern SJV using measurements made as part of California at the Nexus of Air Quality and Climate Change in 2010 (CalNex-SJV). We find the daytime speciated organic reactivity with respect to OH during CalNex-SJV has a temperature-independent portion with molecules typically associated with motor vehicles being the major component. At high temperatures, characteristic of days with high ozone, the largest portion of the total organic reactivity increases exponentially with temperature and is dominated by small, oxygenated organics and molecules that are unidentified. We use this simple temperature classification to consider changes in organic emissions over the last and next decade. With the CalNex-SJV observations as constraints, we examine the sensitivity of ozone production (PO3) to future NOx and organic reactivity controls. We find that PO3 is NOx-limited at all temperatures on weekends and on weekdays when daily maximum temperatures are greater than 29 °C. As a consequence, NOx reductions are the most effective control option for reducing the frequency of future ozone violations in the southern SJV. © 2014 Author(s).