A Multivariable Model for Atmospheric Dispersion Predictions

In conjunction with a 15-month air quality survey of Jacksonville, Fia., a mathematical model has been developed to describe the dispersion of atmospheric pollutants. The source inventory used with the model was compiled, in part, from the data obtained from the sampling of all major sources within the area. The major sources were considered separately from the one-mile square area sources which accounted for the remainder of the emissions. Meteorological data was recorded continuously in the city including vertical temperature observations to 750 ft. The model was compiled in FORTRAN and can be used for both gaseous and particulate pollutants, by utilizing proper decay rates. The variant nature of meteorological parameters and emission rates are considered. The ground level concentrations of several pollutants which were determined for 24 hr periods at 11 sites and continuously at two other sites were used to check the model. A limited tracer study was carried out in conjunction with the project.     

A Simplified Technique Used to Evaluate Atmospheric Dispersion of Emissions from Large Power Plants

A simplified method which is used by the Tennessee Valley Authority to estimate ambient concentrations of atmospheric emissions from its large power plants is presented. The technique requires the use of three nomogrdms for the rapid graphic solution of three dispersion models—coning, inversion breakup, and trapping. A discussion of the meteorological conditions that are associated with these dispersion models, supporting appendices, and a worked example are also presented.     

Simulating industrial emissions using Atmospheric Dispersion Modeling System: Model performance and source emission factors

In this paper, the Gaussian Atmospheric Dispersion Modeling System (ADMS4) was coupled with field observations of surface meteorology and concentrations of several air quality indicators (nitrogen oxides (NO_X), carbon monoxide (CO), fine particulate matter (PM₁₀) and sulfur dioxide (SO₂)) to test the applicability of source emission factors set by the European Environment Agency (EEA) and the United States Environmental Protection Agency (USEPA) at an industrial complex. Best emission factors and data groupings based on receptor location, type of terrain and wind speed, were relied upon to examine model performance using statistical analyses of simulated and observed data. The model performance was deemed satisfactory for several scenarios when receptors were located at downwind sites with index of agreement d values reaching 0.58, fractional bias “FB” and geometric mean bias “MG” values approaching 0 and 1, respectively, and normalized mean square error “NMSE” values as low as 2.17. However, median ratios of predicted to observed concentrations “Cp/Co” at variable downstream distances were 0.01, 0.36, 0.76 and 0.19 for NO_X, CO, PM₁₀ and SO₂, respectively, and the fraction of predictions within a factor of two of observations “FAC2” values were lower than 0.5, indicating that the model could not adequately replicate all observed variations in emittant concentrations. Also, the model was found to be significantly sensitive to the input emission factor bringing into light the deficiency in regulatory compliance modeling which often uses internationally reported emission factors without testing their applicability.

Implications In the absence of site-specific source emission factors, the use of internationally reported emission factors without testing their validity may generate significant errors. Instead, recorded field measurements and meteorological data may be combined with atmospheric transport and dispersion models to better estimate source emissions, particularly in regulatory compliance studies. In this context, lower model performance is expected at higher wind speeds for most indicators such as CO, PM₁₀, and SO₂.     

HCI in Rocket Exhaust Clouds: Atmospheric Dispersion,Acid Aerosol Characteristics,and Acid Rain Deposition

NASA is examining Space Shuttle launch impacts. Solid rocket exhaust includes ?60 tons HCL and ?87 tons alumina particles emitted below 2.5 km, of which 50-80% forms an altitude stabilized exhaust cloud (EC). Several 60% smaller Titan-Ill EC were sampled by aircraft for this study. Three distinct features are presented: (a) An analysis of HCL (gaseous plus aqueous) data traces. Total range of peak HCL was 25-0.5 ppm (3-300 min) for 8 EC. Power-law decays of peak HCL applied. Calculated HCL dispersions for 7 standard meteorologies are also shown, (b) An analysis of simultaneous HCL (g), HCL (g + aq) data for 2 EC. Vapor-liquid HCL/H₂O equilibria were calculated for a flat surface aqueous aerosol. HCL partitioning varied with EC dilution and H₂O content. HCL (aq) and aqueous mass fraction maximized early at >3 molal and >0.1 mg/g air. Calculated H₂O (g + aq) compared favorably with independent EC measurements, (c) An analysis of wet deposition after EC interception at ?30 min by a convective storm. A 28 km² acid chloride (1 < pH < 3) footprint was defined. In conclusion, (a) HCL dispersion in large EC tends to follow power-law decay, but HCL concentration may vary widely (100 times after 1 h) with meteorology, (b) HCL (g/aq) and H₂O (g/aq) partitioning is consistent with equilibrated acid aerosol compositions, and (c) localized deposition of highly acidic rain may occur sometimes.     

Atmospheric corrosion effects of HNO3—Influence of temperature and relative humidity on laboratory-exposed copper

The effect of HNO₃ on the atmospheric corrosion of copper has been investigated at varied temperature (15–35 °C) and relative humidity (0–85% RH). Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) confirmed the existence of cuprite and gerhardtite as the two main corrosion products on the exposed copper surface. For determination of the corrosion rate and for estimation of the deposition velocity (V_d) of HNO₃ on copper, gravimetry and ion chromatography has been employed. Temperature had a low effect on the corrosion of copper. A minor decrease in the mass gain was observed as the temperature was increased to 35 °C, possibly as an effect of lower amount of cuprite due to a thinner adlayer on the metal surface at 35 °C. The V_d of HNO₃ on copper, however, was unaffected by temperature. The corrosion rate and V_d of HNO₃ on copper was the lowest at 0% RH, i. e. dry condition, and increased considerably when changing to 40% RH. A maximum was reached at 65% RH and the mass gain remained constant when the RH was increased to 85% RH. The V_d of HNO₃ on copper at ⩾65% RH, 25 °C and 0.03 cm s⁻¹ air velocity was as high as 0.15±0.03 cm s⁻¹ to be compared with the value obtained for an ideal absorbent, 0.19±0.02 cm s⁻¹. At sub-ppm levels of HNO₃, the corrosion rate of copper decreased after 14 d and the growth of the oxide levelled off after 7 d of exposure.     

Methyl Tertiary Hexyl Ether and Methyl Tertiary Octyl Ether as Gasoline Oxygenates: Assessing Risks from Atmospheric Dispersion and Deposition

Abstract

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10^?3 and 10^?2 for MtHxE and MtOcE, respectively, in Boston, and 10^?2 and 10^?1 in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.     

Direct Effects of Atmospheric Sulfate Deposition on Vegetation

Acid sulfate aerosol (500 μg/m³) had no effect on soybean or pinto bean after a single 4-h exposure. However, visible Injury and chlorophyll loss occurred when plants were sequentially exposed to acid aerosol and ozone (380 μg/m³) for 4 h. In yellow poplar seedlings exposed to ozone (200 μg/m³), sulfur dioxide (210 μg/m³) and simulated rain solutions (pH 5.6, 4.3 and 3.0) for 6 weeks, root dry weight, leaf area increase, mean relative growth rate and unit leaf rate decreased linearly with pH in ozone-treated plants. However, unit leaf rate and mean relative growth rate increased linearly in response to sulfur dioxide as solution acidity increased. Ambient wet and dry sulfate concentrations appear insufficient to directly impact vegetation.     

Some Effects of Atmospheric Fluoride on Plant Metabolism

Leaves of Tendergreen bean plants exposed to atmospheric fluoride concentrations in the range 1.7 to 7.6 μg/m³ showed increased levels of enolase and catalase activity and decreased levels of pyruvate and α-ketoglutarate. Phosphoenolpyruvate carboxylase activity and oxalacetate were not affected. The leaves of Milo maize plants exposed to 5.0 μg F/m³ showed increased levels of enolase and pyruvate kinase activity and a decreased level of pyruvate. Oxalacetate and α-ketoglutarate levels were not affected. Catalase activity was increased, then decreased by IIF fumigation. The changes induced by HF were greatest six to 10 days after the start of fumigation and disappeared or decreased in magnitude during the post-fumigation period.     

Chemistry of Atmospheric Oxidants

All of the important oxidants in polluted air are formed there by chemical reactions which occur among the primary pollutants. The most abundant of these oxidants is ozone which is formed in a cycle involving nitric oxide, nitrogen dioxide, atmospheric oxygen, and hydrocarbons. This ozone is best understood, not as a reaction product, but as an intermediate in steady-state concentration between formation and disappearance reactions. Hydrocarbons permit accumulation of ozone by reacting to scavenge the nitric oxide which would otherwise remove the ozone. The amount of ozone which can be formed in ambient polluted air is limited to about 1 ppm because these scavenging reactions become less effective when the nitric oxide concentration becomes very small. The peroxyacyl nitrates are a group of oxidants which result from reactions between oxides of nitrogen and organic pollutants. Olefinic and aromatic hydrocarbons make the largest contribution to PAN formation; saturates contribute little if any. The role of nitrogen dioxide and other oxidizing agents is also discussed.     

Atmospheric Chemistry of Toxic Contaminants 1. Reaction Rates and Atmospheric Persistence

Using structure-reactivity relationships between reaction rate constants and ionlzatlon potentials for structural homologues, estimates are presented for the rate constants of the reactions of ozone, the hydroxyl radical, and the nitrate radical with forty toxic air contaminants for which no or little data are available. These rate constants are in turn used to estimate the atmospheric persistence of saturated allphatics, unsaturated allphatics, and aromatic toxic organics. The corresponding atmospheric half-lives for removal by chemical reactions range from a few hours for the most reactive toxics (chloroprene, hexachlorocyclo-pentadiene, cresols, nitrosamines, maleic anhydride) to several months for the least reactive compounds (nitrobenzene, methyl bromide, phosgene).     

Physiological and Biochemical Effects of Atmospheric Oxidants on Plants

Photochemically produced oxidants in the atmosphere cause injury to plants primarily through inhibition of basic metabolic processes. Plants vary in their response to the oxidants and this variation must be dependent in part on the variation in metabolic activity with age or environmental conditions for growth, to a large degree not understood. Data are presented in this paper to show: (1) The changes in permeability of leaf tissue to exogenous substrate and in catabolic utilization of this substrate after exposure of plants to ozone but before visible symptoms appear; (2) The change in leaf carbohydrates as a result of exposure to ozone; (3) The protective effect of red light (700 mμ) during exposure of bean plants to peroxyacetyl nitrate (PAN); (4) The correlation of sulfhydryl (SH) content in bean leaf tissue with age of plants and light regime; and (5) Effect of light regime and age of plants on incorporation of C¹⁴ from C¹⁴-PAN by bean leaf tissue.     

Effects of Atmospheric Nitrogen Deposition on Remote Freshwater Ecosystems

We review known and hypothesized effects of nitrogen (N) deposition owing to human activities on the chemistry, organisms, and ecosystem processes of remote oligotrophic freshwaters. Acidification is the best-known effect of N deposition on water chemistry, but additional effects include increased nutrient availability and alteration of the balance between N and other nutrients. Our synthesis of the literature, framed in a comprehensive model for the effects of N deposition on natural ecosystems, shows that all these effects can reduce biological diversity and alter ecosystem processes in remote freshwaters. N deposition is projected to grow worldwide in the near future and will interact with other global changes. Present effects on these fragile ecosystems may be only early signs of more radical impacts ahead.     

Atmospheric ozone: formation and effects on vegetation

Ozone (O(3)) is present both in the troposphere and the stratosphere. Troposphere O(3) is predominantly produced by photochemical reactions involving precursors generated by natural processes and to a much larger extent by man's activities. There is evidence for a trend towards increasing tropospheric O(3) concentrations. However, tropospheric O(3) is known to account for only 10% of the vertical O(3) column above the earth's surface. The stratosphere accounts for an additional 90% of the O(3) column. There is evidence to suggest that there are losses in the stratospheric O(3) due to the updraft of O(3) destroying pollutants generated by both natural processes and by human activity. Such a loss in stratospheric O(3) can result in alterations of incidence in the ultraviolet (UV) radiation to the earth's surface. Tropospheric O(3) is known to be highly phytotoxic. Appropriate exposures to O(3) can result in both acute (symptomatic) and chronic (changes in growth, yield or productivity and quality) effects. Chronic effects are of great concern in terms of both crops and forests. A number of experimental techniques are available to evaluate the chronic effects of O(3) on plants. There are limitations attached to the use of these techniques. However, results obtained, with such techniques are valuable if interpreted in the appropriate context. Among all field evaluation techniques, open-top chambers are the most frequently used method for evaluating the chronic effects of O(3) on crops. The National Crop Loss Assessment Program (NCLAN) of the United States is the largest such effort. However, given the limitations of the open-top chambers and the experimental aspects of NCLAN, its results must be interpreted with caution. On the other hand, acute effects can be evaluated with less complexity through the use of biological indicator plants. The numerical modelling of such effects are also far less complicated than establishing numerical cause and effects relationships for chronic effects. Confounding the acute or chronic responses of plants to O(3), is the presence of other kinds and forms of pollutants in the ambient atmosphere and the incidence of pathogens and pests. The resulting complex interactions and joint effects on plants are poorly understood. Future research must address these issues. In the final analysis we have re-emphasized the fact that plant health is the product of its interaction with the physical and chemical climatology and pathogens and pests. What we have described in this context is the importance of tropospheric O(3) within the chemical climatology of our environment and its effects on vegetation.     

Atmospheric chemistry of 1,1,1,2-tetrafluoroethane

A one-dimensional eddy diffusion model was used to investigate the fate of 1,1,1,2-tetrafluoroethane (F-134a) in the atmosphere. The substitution of F-134a for F-12 (CF₂Cl₂) used in mobile air conditioning applications would eliminate the possibility of chlorine-related stratospheric ozone depletion from those applications and would introduce no more, and probably less, hydrogen fluoride (HF) into the stratosphere than the continued use of F-12. Such a substitution would only be possible if a commercial process is developed which can produce F-134a in suitable quantities.     

Atmospheric Chemistry of Chlorinated Phenols

The quantum yields for the photodegradation of a series of chlorophenols have been used to estimate their rates of solar photodegradation In the atmosphere. The photochemical rates have been compared with the calculated rates of attack by atmospheric hydroxyl radicals. These two processes are complementary, with photolysis being faster for pentachlorophenol, and OH attack being faster for monochlorinated phenols. As a result, it is predicted that most chlorophenol congeners will have quite similar atmospheric half-lives.