Ammonia flux from open-lot dairies: development of measurement methodology and emission factors.

Ammonia emissions contribute to the formation of secondary particulate matter (PM) and violations of the National Ambient Air Quality Standard. Ammonia mass concentration measurements were made in February 1999 upwind and downwind of an open-lot dairy in California, using a combination of active bubbler and passive filter samplers. Ammonia fluxes were calculated from concentrations measured at 2, 4, and 10 m above ground at three locations on the downwind edge of the dairy, using micrometeorological techniques. A new method was developed to interpolate fluxes at six additional locations from ammonia concentrations measured at a single height, providing measurements at sufficient spatial resolution along the downwind border of the dairy to account for the heterogeneity of the source. PM measured up- and downwind of the dairy demonstrated insignificant ammonium particle formation in the immediate vicinity of the dairy and negligible contribution of dissociated ammonium nitrate to measured ammonia concentrations. Ammonium nitrate concentrations measured downwind of the dairy ranged from 26 to 0.26 microg m(-3) and from 2 to 43% of total PM2.5 mass concentrations. Measured ammonia fluxes showed that liquid manure retention ponds represented relatively minor sources of ammonia in winter on the dairy studied. Ammonia emission factors derived from the measurements ranged from 19 to 143 g head(-1) day(-1), showing an increase with warmer, drier weather and a decrease with increased relative humidity and lower temperatures.

Ammonia emission factors for open-lot dairies: direct measurements and estimation by nitrogen intake.

Ammonia (NH3) emissions contribute to the formation of secondary particulate matter (PM) 10 microm and under (PM10). Dairies are significant sources of NH3 in the San Joaquin Valley (SJV) of California, where the National Ambient Air Quality Standard for PM10 is frequently exceeded. Detailed descriptions of diets, animal demographics, and production levels were obtained for two commercial open-lot dairies in the SJV and used to compute nitrogen intake for each feeding group (g N day(-1)). Models derived from nutrition trials with cows, heifers, and calves were used to estimate urea-N excretion from N intake. Air NH3 concentrations were also measured at the same dairies over 1-week periods in February 1999. NH3 fluxes calculated from vertical profiles of concentrations at two or three locations downwind of the dairies were augmented with estimates of flux based on single-height concentrations measured at five or six additional downwind locations to compute NH3 emission rates. NH3 emission potentials, estimated from urea-N excretion, exceeded NH3 emission rates measured by the micrometeorological methods by 1.5- and 3-fold on the two dairies. A diurnal pattern in NH3 emission factors based on measurements showed peak emission occurring between 1:00 p.m. and 6:00 p.m. at both dairies. NH3 emission potentials and measured NH3 emission rates were higher for Dairy 2, which reported feeding heifers dietary crude protein in excess of National Research Council recommendations.

Spatial, temporal, and interspecies patterns in fine particulate matter in Texas.

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) field study was conducted from July to October 1999 and was followed by several years of modeling and data analyses to examine the causes of haze at Big Bend National Park TX (BBNP). During BRAVO, daily speciated fine (diameter <2.5 microm) particulate concentrations were measured at 37 sites throughout Texas. At the primary receptor site, K-Bar Ranch, there were many additional measurements including a "high-sensitivity" version of the 24-hr fine particulate elemental data. The spatial, temporal, and interspecies patterns in these data are examined here to qualitatively investigate source regions and source types influencing the fine particulate concentrations in Texas with an emphasis on sources of sulfates, the largest contributor to fine mass and light extinction. Peak values of particulate sulfur (S) varied spatially and seasonally. Maximum S was in Northeast Texas during the summer, whereas peak S at BBNP was in the fall. Sulfate acidity at BBNP also varied by month. Sources of Se were evident in Northeast Texas and from the Carbón I and II plants. High S episodes at BBNP during BRAVO had several different trace element characteristics. Carbon concentrations at BBNP during BRAVO were probably mostly urban-related, with arrival from the Houston area likely. The Houston artificial tracer released during the second half of BRAVO was highly correlated with some carbon fractions. There was evidence of the influence of African dust at sites throughout Texas during the summer. Patterns in several trace elements were also examined. Vanadium was associated with air masses from Mexico. Lead concentrations in southern Texas have dropped dramatically over the past several years.

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.

Loss of particle nitrate from teflon sampling filters: effects on measured gravimetric mass in California and in the IMPROVE network.

The extent of mass loss on Teflon filters caused by ammonium nitrate volatilization can be a substantial fraction of the measured particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) or 10 microm (PM10) mass and depends on where and when it was collected. There is no straightforward method to correct for the mass loss using routine monitoring data. In southern California during the California Acid Deposition Monitoring Program, 30-40% of the gravimetric PM2.5 mass was lost during summer daytime. Lower mass losses occurred at more remote locations. The estimated potential mass loss in the Interagency Monitoring of Protected Visual Environments network was consistent with the measured loss observed in California. The biased mass measurement implies that use of Federal Reference Method data for fine particles may lead to control strategies that are biased toward sources of fugitive dust, other primary particle emission sources, and stable secondary particles (e.g., sulfates). This analysis clearly supports the need for speciated analysis of samples collected in a manner that preserves volatile species. Finally, although there is loss of volatile nitrate (NO3-) from Teflon filters during sampling, the NO3- remaining after collection is quite stable. We found little loss of NO3- from Teflon filters after 2 hr under vacuum and 1 min of heating by a cyclotron proton beam.

Application of the tracer-aerosol gradient interpretive technique to sulfur attribution for the big bend regional aerosol and visibility observational study.

A simple data analysis method called the Tracer-Aerosol Gradient Interpretive Technique (TAGIT) is used to attribute particulate S and SO2 at Big Bend National Park in Texas and nearby areas to local and regional sources. Particulate S at Big Bend is of concern because of its effects on atmospheric visibility. The analysis used particulate S, SO2, and perfluorocarbon tracer data from six 6-hr sampling sites in and near Big Bend National Park. The data were collected in support of the Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study; the field portion was conducted from July through October 1999. Perfluorocarbon tracer was released continuously from a tower at Eagle Pass, TX, approximately 25 km northeast of two large coal-fired power plants (Carbon I and II) in Coahuila, Mexico, and approximately 270 km east-southeast of Big Bend National Park. The perfluorocarbon tracer did not properly represent the location of the emissions from the Carbon power plants for individual 6-hr sampling periods and attributed only 3% of the particulate S and 27% of the SO2 at the 6-hr sites in and near Big Bend to sources represented by the tracer. An alternative approach using SO2 to tag "local" sources such as the Carbon plants attributed 10% of the particulate S and 75% of the SO2 at the 6-hr sites to local sources. Based on these two approaches, most of the regional (65-86%) and a small fraction (19-31%) of the local SO2 was converted to particulate S. The analysis implies that substantial reductions in particulate S at Big Bend National Park cannot be achieved by only reducing emissions from the Carbon power plants; reduction of emissions from many sources over a regional area would be necessary.

Hygroscopic organic aerosols during BRAVO?

The hygroscopic properties of the organic fraction of aerosols are poorly understood. The ability of organic aerosols to absorb water as a function of relative humidity (RH) was examined using data collected during the 1999 Big Bend Regional Aerosol and Visibility Observational Study (BRAVO). (On average, organics accounted for 22% of fine particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5) mass). Hourly RH exceeded 80% only 3.5% of the time and averaged 44%. BRAVO aerosol chemical composition and dry particle size distributions were used to estimate PM2.5 light scattering (Bsp) at low and high ambient RH. Liquid water growth associated with inorganic species was sufficient to account for measured Bsp for RH between 70 and 95%.

Motor Vehicle Emissions Variability.

Test-to-test variability has been observed by many current testing methods, including the Federal Test Procedure, the IM240 dynamometer test, the idle test common to many Inspection and Maintenance programs, and on-road remote sensing. The variability is attributable to the vehicle, not to the testing procedure. Because the vehicles are the dominant source of variability, the only way such vehicles can be reliably identified is through the use of multiple tests. The emissions variability increases with increasing average emissions, and it appears to be prevalent among the few newer technology vehicles with defective, but untampered, closed-loop emissions control systems (1981 and newer models). In one fleet the variable emitters constitute 2.2% to 4.8% of the vehicles and contribute 8.5% to 22% of the total carbon monoxide emissions. Scheduled I/M programs that fail to ensure repair of these vehicles allow a significant portion of vehicles with excess emissions to escape reduction measures.

Resuspension of soil as a source of airborne lead near industrial facilities and highways.

Geologic materials are an important source of airborne particulate matter less than 10 microm aerodynamic diameter (PM10), but the contribution of contaminated soil to concentrations of Pb and other trace elements in air has not been documented. To examine the potential significance of this mechanism, surface soil samples with a range of bulk soil Pb concentrations were obtained near five industrial facilities and along roadsides and were resuspended in a specially designed laboratory chamber. The concentration of Pb and other trace elements was measured in the bulk soil, in soil size fractions, and in PM10 generated during resuspension of soils and fractions. Average yields of PM10 from dry soils ranged from 0.169 to 0.869 mg of PM10/g of soil. Yields declined approximately linearly with increasing geometric mean particle size of the bulk soil. The resulting PM10 had average Pb concentrations as high as 2283 mg/kg for samples from a secondary Pb smelter. Pb was enriched in PM10 by 5.36-88.7 times as compared with uncontaminated California soils. Total production of PM10 bound Pb from the soil samples varied between 0.012 and 1.2 mg of Pb/kg of bulk soil. During a relatively large erosion event, a contaminated site might contribute approximately 300 ng/m3 of PM10-bound Pb to air. Contribution of soil from contaminated sites to airborne element balances thus deserves consideration when constructing receptor models for source apportionment or attempting to control airborne Pb emissions.

Source Apportionment of Soil Samples by the Combination of Two Neural Networks Based on Computer-Controlled Scanning Electron Microscopy.

The apportionment of ambient aerosol mass to different sources of airborne soil is a difficult problem because of the similarity of the chemical composition of crustal sources. However, additional information can be obtained using individual particle analysis. A novel approach based on the combination of two neural networks, the adaptive resonance theory-based neural network (ART-2a) and the back-propagation (BP) neural network with electron microscopy data, has been developed to apportion the mass contributions of the crustal sources to ambient particle samples. The crustal source samples were analyzed using computer-controlled scanning electron microscopy (CCSEM). CCSEM provides elemental compositions and size parameters for individual particles as well as estimates of the shape and density from which the volume and mass of each particle can be estimated. The ART-2a neural network was first used to partition particles into homogeneous classes based on the elemental composition data. After the different particle type classes were produced by ART-2a, their mass fractions were calculated. In this way, the source profiles for the crustal dust sources can be obtained in terms of the mass fractions for different particle types. Then the BP neural network was applied to build the model between the mass fractions of different particle types and the mass contributions. Using the three physical source samples prepared for this study, artificial ambient samples were generated by randomly mixing particles from the three source samples. These samples were then used to examine the proposed method. Satisfactory predictions for the mass contributions of the three sources to the ambient samples have been obtained, indicating the proposed method is a promising tool for the source apportionment of chemically similar soil samples.