Determination of volatile organic compound emissions and ozone formation from spraying solvent-based pesticides.

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.

Direct measurements of the ozone formation potential from livestock and poultry waste emissions.

The global pattern of expanding urban centers and increasing agricultural intensity is leading to more frequent interactions between air pollution emissions from urban and agricultural sources. The confluence of these emissions that traditionally have been separated by hundreds of kilometers is creating new air quality challenges in numerous regions across the United States. An area of particular interest is California's San Joaquin Valley (SJV), which has an agricultural output higher than many countries, a rapidly expanding human population, and ozone concentrations that are already higher than many dense urban areas. New regulations in the SJV restrict emissions of reactive organic gases (ROGs) from animal sources in an attempt to meet Federal and State ozone standards designed to protect human health. The objective of this work is to directly measure the ozone formation potential (OFP) of agricultural animal plus waste sources in representative urban and rural atmospheres using a transportable "smog" chamber. Four animal types were examined: beef cattle, dairy cattle, swine, and poultry. Emissions from each animal plus waste type were captured in a 1 m(3) Teflon bag, mixed with representative background NO(x) and ROG concentrations, and then exposed to UV radiation so that ozone formation could be quantified. The emitted ROG composition was also measured so that the theoretical incremental reactivity could be calculated for a variety of atmospheres and directly compared with the measured OFP under the experimental conditions. The results demonstrate that OFP associated with waste ROG emissions from swine (0.39 +/- 0.04 g-O(3) per g-ROG), beef cattle (0.51 +/- 0.10 g-O(3) per g-ROG), and dairy cattle (0.42 +/- 0.07 g-O(3) per g-ROG) are lower than OFP associated with ROG emissions from gasoline powered light-duty vehicles (LDV) (0.69 +/- 0.05 g-O(3) per g-ROG). The OFP of ROG emitted from poultry waste (1.35 +/- 0.73 g-O(3) per g-ROG) is approximately double the LDV OFP. The measured composition of ROG emitted from animal plus waste sources is nine times less reactive than the current regulatory profiles that are based on dated measurements. The new animal waste ROG OFP measurements combined with adjusted animal waste ROG emissions inventory estimates predict that actual ozone production in the SJV from livestock and poultry (5.7 +/- 1.3 tons O(3) day(-1)) is 40 +/- 10% of the ozone produced by light duty gasoline vehicles (14.3 +/- 1.4 tons O(3) day(-1)) under constant NO(x) conditions.

Reactive organic gas emissions from livestock feed contribute significantly to ozone production in central California.

The San Joaquin Valley (SJV) in California currently experiences some of the highest surface ozone (O(3)) concentrations in the United States even though it has a population density that is an order of magnitude lower than many urban areas with similar ozone problems. Previously unrecognized agricultural emissions may explain why O(3) concentrations in the SJV have not responded to traditional emissions control programs. In the present study, the ozone formation potentials (OFP) of livestock feed emissions were measured on representative field samples using a transportable smog chamber. Seven feeds were considered: cereal silage (wheat grain and oat grain), alfalfa silage, corn silage, high moisture ground corn (HMGC), almond shells, almond hulls, and total mixed ration (TMR = 55% corn silage, 16% corn grain, 8% almond hulls, 7% hay, 7% bran + seeds, and 5% protein + vitamins + minerals). The measured short-term OFP for each gram of reactive organic gas (ROG) emissions from all livestock feed was 0.17-0.41 g-O(3) per g-ROG. For reference, OFP of exhaust from light duty gasoline powered cars under the same conditions is 0.69 +/- 0.15 g-O(3) per g-ROG. Model calculations were able to reproduce the ozone formation from animal feeds indicating that the measured ROG compounds account for the observed ozone formation (i.e., ozone closure was achieved). Ethanol and other alcohol species accounted for more than 50% of the ozone formation for most types of feed. Aldehydes were also significant contributors for cereal silage, high moisture ground corn, and total mixed ration. Ozone production calculations based on feed consumption rates, ROG emissions rates, and OFP predict that animal feed emissions dominate the ROG contributions to ozone formation in the SJV with total production of 25 +/- 10 t O(3) day(-1). The next most significant ROG source of ozone production in the SJV is estimated to be light duty vehicles with total production of 14.3 +/- 1.4 t O(3) day(-1). The majority of the animal feed ozone formation is attributed to corn silage. Future work should be conducted to reduce the uncertainty of ROG emissions from animal feeds in the SJV and to include this significant source of ozone formation in regional airshed models.

Analysis of aerosol particles and coarse particulate matter concentrations in Chillán, Chile, 2001-2003.

Daily particle samples were collected in Chillán, Chile, at six urban locations from September 1, 2001, through September 30, 2003. Aerosol samples were collected using monitors equipped with a Sierra Andersen 246-b cyclone inlet on Teflon filters. Average concentrations of coarse particulate matter (PM10) for the 2001-2003 period ranged from 43.4 microg/m3 to 81.8 microg/m3 across the six sites. Annual PM10 concentration levels exceeded the European Union concentration limits. Mean PM10 levels during the cold season (April through September) were more than twice as high as those observed in the warm season (October through March). Average contributions to PM10 from organic matter, soil dust, nitrate (NO3-), elemental carbon, ammonium (NH4+), and sulfate (SO4(2-)) were 31%, 27%, 11%, 8%, 7%, and 5%, respectively. The chemical analyses indicated that carbonaceous substances were the most abundant components of PM10 in cold months, whereas crustal material was the most abundant component of PM10 during warm months. Higher concentration levels were observed in the downtown area suggesting a clear anthropogenic origin, whereas in the rural sites the source was mainly natural, such as resuspended soil dust associated with traffic on unpaved roads and agricultural activities.

The application of thermal desorption GC/MS with simultaneous olfactory evaluation for the characterization and quantification of odor compounds from a dairy.

Few analytical methods exist that combine chemical and sensory analysis of odorous compounds in whole air. Volatile organic compounds were collected by sampling air downwind from a small dairy through sorbent tubes of Tenax TA and Carboxen 569. Samples were analyzed by thermal desorption into a cryotrap and subsequent gas chromatographic separation, followed by simultaneous olfactometry and mass spectrometry. Because compounds are concentrated during sampling, sensory analysis encountered compounds at a concentration 40 times that in air, making this a useful method for identifying trace compounds participating in odor. Twenty odorous and nonodorous compounds were identified and quantified, including straight-chain and aromatic hydrocarbons, chlorinated compounds, alcohols, ketones, aldehydes, and organic acids, at air concentrations of 0.55-320.20 microg/m(3). Compound peaks were characterized by odors ranging from offensive to pleasant, demonstrating the integrative nature of olfaction. This method could be useful in studying many kinds of odors in air.