The Relationship between Cross-Sectional and Time Series Studies

Abstract

There is a dearth of information on dust emissions from sources that are unique to the U.S. Department of Defense testing and training activities. However, accurate emissions factors are needed for these sources so that military installations can prepare accurate particulate matter (PM) emission inventories. One such source, coarse and fine PM (PM₁₀ and PM_2.5) emissions from artillery backblast testing on improved gun positions, was characterized at the Yuma Proving Ground near Yuma, AZ, in October 2005. Fugitive emissions are created by the shockwave from artillery pieces, which ejects dust from the surface on which the artillery is resting. Other contributions of PM can be attributed to the combustion of the propellants. For a 155–mm howitzer firing a range of propellant charges or zones, amounts of emitted PM₁₀ ranged from ～19 g of PM₁₀ per firing event for a zone 1 charge to 92 g of PM₁₀ per firing event for a zone 5. The corresponding rates for PM_2.5 were ～9 g of PM_2.5 and 49 g of PM_2.5 per firing. The average measured emission rates for PM₁₀ and PM_2.5 appear to scale with the zone charge value. The measurements show that the estimated annual contributions of PM₁₀ (52.2 t) and PM_2.5 (28.5 t) from artillery backblast are insignificant in the context of the 2002 U.S. Environment Protection Agency (EPA) PM emission inventory. Using national–level activity data for artillery fire, the most conservative estimate is that backblast would contribute the equivalent of 5 x 10^–4% and 1.6 x 10^–3% of the annual total PM₁₀ and PM_2.5 fugitive dust contributions, respectively, based on 2002 EPA inventory data.     

A Collaborative Effort to Model Plant Response to Acidic Rain

Radish plants were exposed three times per week to simulated acidic rain at pH values of 2.6 to 5.4 over the course of four weeks in trials performed at Argonne, Illinois; Ithaca and Upton, New York; Corvallis, Oregon; Oak Ridge, Tennessee; and Toronto, Canada. Uniform genotype, soil media and planting techniques, treatment procedures, biological measurements, and experimental design were employed. Growth of plants differed among trials as a result of variation in greenhouse environmental conditions according to location and facilities. Larger plants underwent greater absolute but lower relative reductions in biomass after exposure to the higher levels of acidity. A generalized Mitscherlich function was used to model the effects of acidity of simulated rain or dry mass of hypocotyls using data from three laboratories that performed duplicate trials. The remaining data, from three other laboratories that performed only one trial each, were used to test the model. When the laboratory by trial effect was removed (influence of different growth. conditions), lack of fit to the Mitscherlich function was insignificant. Thus, a single mathematical model satisfactorily characterized the relationship between acidity and mean plant response. The pH value associated with a 10 percent reduction in mass was 3.3 ± 0.3 for hypocotyls. No value was estimated for shoots because effects oh shoots were not significant. The results of this study demonstrate that a generalized exposure-response model can be developed in the presence of large variations in environmental conditions when plant culture and exposure to simulated rain are standardized among laboratories.     

Reducing Interference Effects in the Chemiluminescent Measurement of Nitric Oxides from Combustion Systems

Experiments were carried out to determine the relative chemiluminescence quenching efficiencies as a function of third body concentration for each of the common combustion products, H₂O, CO₂, CO, H₂, O₂ and Ar. These results are compared with those of other investigators. The effect of reaction chamber pressure on analyzer response and the development of an analyzer design which incorporates an adjustable sample capillary inlet capable of maintaining a constant molar flow rate of sample gas to the reaction chamber are discussed. The effect of carbon monoxide interference on chemiluminescent NO_x measurement has been isolated and found to be significant. A means of correcting NO, measurements for these CO interference effects is described. Quantification of NO and NO₂ absorption in liquid water in NO_x sampling systems has been made. Recommendations for sample system designs to handle the presence of water in the sample gas are made.     

KAPPA-G,A Non-Gaussian Plume Dispersion Model: Description and Evaluation Against Tracer Measurements

This paper presents a mixed methodology for the simulation of atmospheric disperson phenomena in which vertical diffusion is computed using an analytical solution of the K-theory equation, while horizontal diffusion is simulated by the Gaussian formula. This new formulation, while maintaining a simple analytical form for the concentration field, incorporates the effects of power-law vertical profiles of both wind speed and eddy diffusivity. The performance of this approach, which has been implemented into a full computer package (KAPPA-G), is evaluated by comparison with data from SF₆ tracer experiments.     

Numerical Simulation of the Thermal Destruction of Some Chlorinated C1 and C2 Hydrocarbons

We have numerically modeled the breakdown of small quantities of several chlorinated hydrocarbons (CH₃CI, CH₂CI₂, CHCI₃, CCI₄, C₂H₃CI, and C₂H₅CI) in a lean mixture of combustion products between 800 and 1480 K. This simulates the fate of poorly atomized waste in a liquid-Injection Incinerator. Kinetics calculations were performed using the CHEMKIN and SENKIN programs, with a reaction mechanism that was developed at Louisiana State University to model flat-flame burner experiments.

A 99.99-percent destruction efficiency was attained In one second at temperatures ranging from 1280 to 960 K, with CCI4 requiring the highest temperature for destruction and C₂H₅CI the lowest. For all compounds except C₂H₅CI, there was a range of temperatures at which byproducts accounted for several percent of the elemental chlorine at the outlet. The more heavily chlorinated compounds formed more byproducts even though the amount of elemental chlorine was the same in all cases. The sensitivity of results to residence time, equivalence ratio, temperature profile, and the presence of additional chlorine, was examined for the case of CHCI₃.     

Nonmethane Organic Compound to Nitrogen Oxide Ratios and Organic Composition in Cities and Rural Areas

The observed ranges in nonmethane organic compound (NMOC) concentrations, NMOC composition and nitrogen oxides (NO_X) concentrations have been evaluated for urban and nonurban areas at ground level and aloft of the contiguous United States. The ranges in NMOC to NO_X ratios also are considered. The NMOC composition consistently shifts towards less reactive compounds, especially the alkanes, in air parcels over nonurban areas compared to the NMOC composition near ground level within urban areas. The values for the NMOC to NO_X ratios, 1.2 to 4.2, in air aloft over nonurban areas are lower than in air at ground level urban sites, ≥8, and much lower than in air at ground level nonurban sites, ≥20.

The layers of air aloft over a number of nonurban areas of the United States tend to accumulate NO_X emissions from the tall stacks of large fossil fuel power plants located at nonurban sites. During the night into the morning hours, the air aloft is isolated from any fresh NMOC emissions predominately coming from near surface sources. Conversely, during this extended period of restricted vertical mixing, air near the surface accumulates NMOC emissions while this air is isolated from the major NO_X sources emitting aloft. These differences in the distribution of NMOC and NO_X sources appear to account for the much larger NMOC to NO_X ratios reported near ground level compared to aloft over nonurban areas.

Two types of experimental results are consistent with these conclusions: (1) observed increases in surface rural NO_X concentrations during the morning hours during which the mixing depth increases to reach the altitude at which NO_X from the stacks of fossil fuel power plants is being transported downwind; (2) high correlations of total nitrate at rural locations with Se, which is a tracer for coal-fired power plant NO_X emissions.

The implications of these conclusions from the standpoint of air quality strategies are suggested by use of appropriate scenarios applied to both urban and regional scale photochemical air quality models. The predictions from urban model scenarios with NMOC to NO_X ratios up to 20 are that NO_X control will result in the need for the control of more NMOC emissions than necessary in the absence of NO_X control, in order to meet the O₃ standard. On a regional scale, control of NO_X emissions from fossil fuel power plants has little overall effect regionally but does result on a more local scale in both small decreases and increases in O₃ concentrations compared to the baseline scenario without NO_X control. The regional modeling results obtained to date suggest that NO_X control may be effective in reducing O₃ concentrations only for a very limited set of conditions in rural areas.     

Indoor/Outdoor Measurements of Volatile Organic Compounds in the Kanawha Valley of West Virginia

The Kanawha Valley region of West Virginia which is comprised of Charleston and surrounding communities Is the center of a heavily industrialized area known for its chemical manufacturing. As part of a larger study designed to investigate the Impact of the chemical industry on human exposures to volatile organic compounds (VOC), a study of the relationship between indoor and outdoor concentrations was conducted. Thirty-five homes were selected for monitoring from among volunteers; approximately ten in each of three distinct population-industry centers and four outside the Valley to act as controls. Monitoring was performed using passive, badge samplers with a three-week monitoring period. Two separate questionnaires were administered: one for characterization of the residence; and one to characterize source use during monitoring. Participants were also asked to keep a record of their activities with respect to in-home, outdoors and other Indoor environments. Analysis of the samplers was performed by solvent extraction followed by gas chromatography using a flame-ionization detector. Results suggest that indoor VOC concentrations are higher than outdoor concentrations. Additionally, certain ventilation-related parameters were identified that afforded some predictive power for indoor concentrations. No statistically significant differences between regions were identified.     

Exceedances of the National Ambient Air Quality Standard for Ozone Occurring at a “Pristine” Area Site

Abstract

This paper presents a comparative study of the biodegradation of three aromatic volatile compounds in a compost-based biofilter: toluene, xylene, and 1,2,4-trimethyl-benzene, used in the course of this work for the first time in the field of biofiltration. Hence, three identical biofiltration units have been operated at the laboratory scale. During the experiments, nitrogen (as urea) was supplied at various concentrations to each reactor, via irrigated nutrient solutions. A comparative analysis of the results showed that the biodegradability scale followed the degree of substitution around the aromatic ring: toluene > xylene > trimethylbenzene, with 95, 80, and 70% maximum conversions, respectively. In addition, and despite the different removal levels achieved in the three biore-actors, it was established that from a reaction viewpoint, the degradation of the three compounds seemed to follow similar metabolic pathways involving methylcatechol isomers. Finally, by varying the nitrogen input concentrations in the three reactors, three degradation regimes have been highlighted: an N-limitation regime and an N-optimum regime, common to the three solvents, and an N-excess regime, favorable to the colonization of the filter beds by nitrifying species, which particularly affected the xylene and trimethylbenzene biodegradation.     

Hydrocarbon Measurements During the 1992 Southern Oxidants Study Atlanta Intensive: Protocol and Quality Assurance

Abstract

A major component of the Southern Oxidants Study (SOS) 1992 Atlanta Intensive was the measurement of atmospheric nonmethane hydrocarbons. Ambient air samples were collected and analyzed by a network of strategically located automated gas chromatography (GC) systems (field systems). In addition, an extensive canister sampling network was deployed. Combined, more than 3000 chromatograms were recorded. The SOS science team targeted for quantitative analysis 56 compounds which may be substantial contributors to ozone formation or used as air mass tracers. A quality assurance program was instituted to ensure that good measurements were being made throughout the network for each target compound. Common, high-quality standards were used throughout the network. The performance of individual field systems was evaluated during the intensive through the analysis of challenge mixtures. This methodology helped to identify and correct analytical problems as they arose.