Large-scale agricultural activities have come under scrutiny for possible contributions to the emission of ozone precursors. The San Joaquin Valley (SJV) of California is an area with intense agricultural activity that exceeds the federal ozone standards for more than 30 to 40 d yr(-1) and the more stringent state standards for more than 100 d yr(-1). Pesticides are used widely in both agricultural and residential subregions of the SJV, but the largest use, by weight of "active ingredient," is in agriculture. The objective of the study was to determine the role of pesticide application on airborne volatile organic compounds (VOC) concentrations and ozone formation in the SJV. The ozone formation from the pesticide formulation sprayed on commercial orchards was studied using two transportable smog chambers at four application sites during the summers of 2007 and 2008. In addition to the direct measurements of ozone formation, airborne VOC concentrations were measured before and after pesticide spraying using canister and sorbent tube sampling techniques. Soil VOC concentrations were also measured to understand the distribution of VOCs between different environmental compartments. Numerous VOCs were detected in the air and soil samples throughout the experiment but higher molecular weight aromatic hydrocarbons were the primary compounds observed in elevated concentrations immediately after pesticide spraying. Measurements indicate that the ozone concentration formed by VOC downwind of the orchard may increase up to 15 ppb after pesticide application, with a return back to prespray levels after 1 to 2 d.

The use of pesticides in California's agricultural industry plays a role in air quality with emissions of organic compounds thought to contribute to the formation of ground level ozone. Ozone levels in many regions of California exceed the prescribed Federal and State standards every year. The actual contribution from pesticide applications (as well as other agricultural sources) is largely unknown, and relies on assumptions of reactivity and tendency to evaporate. Progress on accurate determinations of either parameter is limited by many factors, including the proprietary nature of formulations. We have developed an approach which can measure the ozone formation potential of many agricultural sources, in the field. This approach was previously validated and described during a recently completed and published study of emissions from dairy cattle, their feed, as well as their fresh waste. With accompanying measurements of the most abundant volatile organic compounds (VOCs) involved there, we showed agreement between laboratory studies, field measurements, and a computer model of atmospheric photochemical reactions that improves upon past efforts, which were limited to urban/industrial VOCs. Our goal is to reach the same level of understanding for VOCs contained in pesticide formulations. Two sets of field experiments were performed to assess the ozone formation potential of pesticide solvents using a set of transportable smog chambers in the summer of 2007. The first set of experiments were conducted for a solvent-based emulsifiable concentrate (EC) base-spray on a one-acre bare field, and the second set of experiments were conducted for an agricultural application of Lorsban 4E in a three-acre citrus orchard. By comparing the upwind and downwind measurements, the experiments indicated that the emission of pesticide solvent after field application led to increased ozone formation. After a 180 min UV exposure, the ozone formation potential measured at the downwind side averaged 14 ppb higher than that of upwind air, while the average difference was around 3 ppb for background levels on both the day before and the day after pesticide spray. Laboratory experiments were also conducted for different doses of EC base with various levels of nitrogen oxides using the transportable smog chambers. The experimental isopleth demonstrates that VOCs emitted from the EC base could result in high ozone formation. Future work will provide full VOC speciation and application of the results in a regional photochemical model to predict ozone impacts.