Photochemical Reactivities of Paraffinic Hydrocarbon-Nitrogen Oxide Mixtures Upon Addition of Propylene or Toluene

Effects associated with photochemical air pollution were measured during irradiation of n-butane-nitrogen oxide or n-butane-ethane-nitrogen oxide mixtures, with small amounts of propylene or toluene added. The effects measured including nitrogen dioxide and oxidant dosages, yields of formaldehyde and peroxy-acetyl nitrate, and eye irritation response. The results obtained clearly show that beneficial effects result from selective changes in hydrocarbon composition as well as from reduction of total hydrocarbon concenfration. Exclusion of olefins and alkylbenzenes was highly effective in reducing oxidant dosage, formaldehyde and peroxyacetyl nitrate concentrations, and eye irritation response. The only penalty was a modest increase in nitrogen dioxide dosage. A large reduction in nitrogen oxide concentration reduced nitrogen dioxide dosage and eye irritation response, but with the penalty of a large increase in oxidant dosage. The desirability of preferentially reducing olefins and alkylbenzenes rather than paraffinic hydrocarbons, acetylene, and benzene is strongly supported by this study. Research and development efforts should be directed toward preferential hydrocarbon control by mechanical or catalytic control     

Cost-Effectiveness of a Photochemical Oxidant Episode Regulation

The precursors used to conduct and the results of a cost-effectiveness study of photochemical oxidant episode control actions for the State of Illinois are analyzed. The method is general enough to be used in analyzing short-term episode regulations in other geographical areas and for other types of pollutants. Real costs and the probable emission reductions of the precursor compounds to oxidant formation, hydrocarbons and nitrogen oxides, are estimated for each of twenty-two control actions and for sets of control actions that are implemented at four episode stages. Control actions affect the use of motor vehicles and parking facilities; scheduling of road repairs; and the operation of manufacturing and other facilities having process emissions, electric power plants, commercial establishments, and refuse incinerators. The actions are analyzed and compared on the basis of relative economic efficiency. The expected annual cost of the regulation and the distribution of cost across sectors are also discussed. The annual cost of the oxidant episode regulation in the Chicago SMSA Is estimated to be $12.9 million; expected annual emission reductions are 1180 ton hydrocarbons and 970 ton nitrogen oxide. It is concluded that the expected cost of the regulation is not overly restrictive if the frequency of major curtailments in manufacturing and transportation is low; the cost is relatively small compared with the estimated annual cost of sulfur dioxide and particulate controls.     

Calculating Air Quality and Its Control

Air quality is shown as a function of averaging times of five minutes to one year for carbon monoxide, hydrocarbons, nitric oxide, nitrogen dioxide, nitrogen oxides, oxidant, and sulfur dioxide in Chicago, Cincinnati, Los Angeles, New Orleans, Philadelphia, San Francisco, and Washington, D. C. Concentrations are approximately lognormally distributed for all pollutants in all cities for all averaging times. Maximum concentration is inversely proportional to averaging time to an exponent. The exponent is a function of the standard geometric deviation. General air quality and control parameters are derived and shown for one example, nitrogen oxides in Washington, D. C. These values are compared to one air quality standard.     

A Combustion Method for the Determination of Solvent Vapors at Low Concentrations in Air

The nitrogen-containing products of smog chamber reactions have been the subject of much controversy. Concern has arisen over nitrogen products because of the almost universally poor nitrogen balance reported for irradiated mixtures of hydrocarbons and nitrogen oxides. Some possible nitrogen-containing products, such as molecular nitrogen, nitrous oxide, and nitroolefins have been investigated and shown to be unimportant. The nitrogen products most often measured are peroxyacetyl nitrate and residual nitrogen dioxide. These two products rarely comprise more than 70% of the initial nitrogen at the end of an experiment, and often account for less than 50%. Previous experiments in which total nitrate was determined in the gas phase and on the vessel walls at the end of irradiation have shown very good nitrogen balances. The assumption has been made that the nitrate arises from nitric acid formed on the walls by adsorbed N₂O₅.

In the work reported here, all major nitrogen-containing compounds have been monitored continuously for the first time. Nitric oxide and nitrogen dioxide have been monitored by chemilumines-cence and automated Saltzman techniques. Methyl, ethyl, and peroxyacetyl nitrate have been determined by gas chromatogra-phy. Two methods, one continuous and one integrated, have been specially developed to measure nitric acid both in the smog chambers and in the atmosphere. Continuous determination of these compounds yields good nitrogen balances throughout the irradiations.

Profiles of the nitrogen-containing species from irradiated HC/ NO_x mixtures are discussed in terms of nitrogen products and nitrogen balance. Differences in product distribution for different hydrocarbon systems are also considered. Using rate information from the nitrogen compound profiles, important reactions leading to nitrogen-containing products are identified. Interference with the chemiluminescent technique by HON0₂, PAN, and C₂H₅ONO₂ is discussed.     

National Air Quality Standards for Automotive Pollutants – A Critical Review

The recently promulgated national air quality standards for carbon monoxide, nitrogen dioxide, hydrocarbons, and photochemical oxidant are critically reviewed.This review indicates that the standards are more restrictive than can be supported by available data.     

Comment on “A Comparative Validation of the RAM and PTMTP Models for Short-Term S02 Concentrations in Two Urban Areas”

The purpose of this paper is to describe oxidant production and transport along the western shore of Lake Michigan. Air quality and meteorological data were collected in this area of the midwest during the summers of 1976–1978 using a ground-based laboratory and an Instrumented aircraft. Ozone, oxides of nitrogen, hydrocarbons (both total and individual), halocarbons, and numerous meteorological parameters were monitored continuously at the ground site near Kenosha, WI. Aircraft measurements included ozone, oxides of nitrogen, condensation nuclei, visual range (nephelometer), sulfur dioxide, temperature, and relative humidity.     

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.     

Photochemical Reactivities of Exhausts from 1966 Model Automobiles Equipped to Reduce Hydrocarbon Emissions

During the summer of 1966, a selected group of automobiles from the Cincinnati phase of the GSA study were used in an irradiation chamber study. The study was conducted to evaluate the photochemical air pollution potential of representative models of the equipped and unequipped automobiles. Only one set of automobiles, the unequipped Chevelles, produced exhaust capable upon irradiation of forming significant levels of oxidant and PAN. Neither the equipped Chevelles nor any of the Fords or Plymouths, whether equipped or unequipped, produced exhaust having the characteristics necessary to form oxidant or PAN upon irradiation. The eye irritation level reported by the panel upon irradiation of exhaust from unequipped Chevelles was much higher than that produced by the irradiated exhausts from any of the other types of automobiles. Overall, there does appear to be some small improvement with respect to eye irritation in comparing equipped with unequipped automobiles. To a large extent, the improvement in the air pollution potential of exhaust from equipped Chevelles compared to the unequipped Chevelles can be attributed to the reduction in the hydrocarbon to nitrogen oxide ratio. The irradiated exhaust from equipped Chevelles, except for aldehyde levels, is about the same in photochemical air pollution potential as are the exhausts from both equipped and unequipped Fords and Plymouths which are maintained under lean operating conditions. Such irradiation chamber measurements are related to exhaust not hydrocarbon reactivities. Hydrocarbon reactivities can be obtained by direct measurement of reactive and nonreactive hydrocarbons in the automotive emissions.     

Smog Chamber Simulation of Los Angeles Pollutant Transport

The body of information presented in this paper is directed to those individuals concerned with the effect of urban pollution on downwind areas. In the absence of any evidence, it has been widely assumed that increasing NO _x emissions have caused oxidant levels to increase downwind of Los Angeles, i.e., Riverside and San Bernardino. This smog chamber study simulated pollutant transport from Los Angeles to the downwind areas by irradiating a typical Los Angeles hydrocarbon/NO _x mixture for extended periods of time. The smog chamber experiments were extended to 22 hours to obtain an integrated light intensity equal to that which occurs in the Los Angeles area. The effects of variations of nitrogen oxide emissions on an aged air mass were examined. The results show that downwind oxidant levels are only slightly affected by large changes in NO _x emissions. However, it is clear that reduced nitrogen oxide emissions will lead to an increase in oxidant in downtown Los Angeles.     

Visibility Regulations

Experiments were conducted to investigate the appearance of contaminants in fluorocarbon-film bags which have been widely used as photochemical reactors and storage containers in air pollution research. Clean air stored in such bags was gradually contaminated by a wide range of heavy hydrocarbons (≥ C₅ ) as well as by nitrogen oxides. Warming a bag dramatically increased the contamination rate for hydrocarbons. The substances observed in the bags appear to have originated in the air outside the bags and appeared in the bags due to the permeability of the film. When a bag was stored in a controlled clean environment, the rate of contamination by hydrocarbons was dramatically reduced. Experiments in which high concentration mixtures of hydrocarbons and nitrogen oxides were stored in the bags likewise showed that some high molecular weight hydrocarbons as well as NO and NO₂ permeate through the bag walls. Decontamination of the bags can be accomplished by storing them in a clean environment.     

An Equilibrium Analysis of Some Chlorinated Hydrocarbons in Stoichiometric to Fuel-rich Post-flame Combustion Environments

The equilibrium composition of product gases from the combustion of chlorinated hydrocarbons (CHC) has been studied for varying ratios of C, H, Cl, and O under stoichiometric to fuel-rich conditions. An interactive, PC-compatible FORTRAN program, STANJAN, was utilized in conjunction with thermochemical data sources to calculate equilibrium compositions of gas mixtures as a function of temperature. The predicted results, when judiciously Interpreted, assist in the understanding of the potential for formation of residual organic substance emissions (ROSEs) in post-flame environments of an incinerator.

Arguments are presented for the potential formation of chlorinated species, which are stable at ambient temperature, if locally fuel-rich mixtures penetrate into the lower temperature zones of an incinerator. ROSEs that have been observed in field tests of incinerators burning chlorinated compounds are predicted to form under the fuel-rich condition. Furthermore, when the equivalence ratio is greater than unity by even a slight amount, the degree of chlorination of product gases increases markedly when the Cl/H ratio also exceeds unity. In that case, time, temperature, turbulence and an overall fuel-lean stoichiometry may not be sufficient to guarantee elimination of measurable levels of chlorinated products. Possible implications of the equilibrium calculations are discussed. Further systematic studies with additional CHCs, nitrogen?, sulfur?, and heavy metal-bearing compounds are recommended as well as continued efforts to carry out kinetic studies.     

Enhancing bioremediation of diesel oil and gasoline in soil amended with an agroindustry sludge

This paper presents a study of the bioremediation of diesel oil and gasoline by a series of controlled laboratory tests. Sludge from an agroindustry was used to enhance bioremediation of both gasoline and diesel oil mixed with a soil mass to compare its efficiency with that of a mineral fertilizer. Effects of soil microbiology and soil mixtures were investigated by means of evolution of CO2, microorganism populations at 90 days, pH at 65 and 95 days, mineral nitrogen, and gas chromatographic analysis of the benzene, toluene, methyl tertiary butyl ether, C8, and C9+total aromatics at the end of the experiments. Treatments containing sludge showed better soil conditions after 170 days of treatment (inorganic nitrogen and microbiota activity) compared with gasoline and diesel oil without amendments. Samples had no detectable traces of the measured hydrocarbons at 170 days of treatment.     

Control of Photochemical Smog by Alteration of Initial Reactant Ratios

This paper is an endeavor to show how several experimenters have quite closely equaled the results of the other, and how the results from these various laboratories can, by a change of coordinate system, be related to each other in a systematic manner. Only after demonstrating where the Los Angeles Civic Center atmosphere is in relation to these coordinates and the contours, or gradients, of these various effects, eye irritation and oxidant, is it possible to predict the photochemical effect of a reduction of olefins (hydrocarbons) or the reduction of nitric oxide. In addition, a study of the variation in eye irritation with irradiation time, demonstrates that the time at which eye irritation measurements are taken is important in understanding the entire photochemical mechanism underlying the “smog” problem in the summertime in Los Angeles     

An observation-based model for analyzing ozone precursor relationships in the urban atmosphere

An Observation-Based Model (OBM) is described, which uses in-situ atmospheric observations to determine the sensitivity of ozone concentrations in an urban atmosphere to changes in the emissions of ozone precursors (i.e., volatile organic compounds and nitrogen oxides). The model is formulated following the concept of Relative Incremental Reactivity (RIR) developed by Carter and Atkinson. In the OBM, however, observed concentrations rather than emission inventories are used to drive the photochemical simulations and thereby ensure that the calculations are carried out for the proper mix of nitrogen oxides and volatile organic compounds. From these calculations, a series of sensitivity factors, or RIRs, are inferred that can be used to (1) determine whether reducing emissions of nitrogen oxide or emissions of hydrocarbons would be most effective in abating ozone in a given urban area, and (2) identify the most critical subset of hydrocarbons present in an urban atmosphere causing ozone exceedances. Because the OBM is relatively easy and inexpensive to operate and makes use of data that are increasingly available, it can be used to analyze a wide array of ozone episodes and, thus, could prove to be a relatively cost-effective tool for the analysis of ozone precursor relationships in an urban atmosphere. On the other hand, because the OBM is diagnostic rather than prognostic, it cannot be used in a predictive mode to estimate exactly how much emission reduction is needed to reduce ozone concentrations. For this reason, the OBM should be viewed as a complement to, rather than a substitute for, more sophisticated gridded, emission-based models. To illustrate the characteristics of the OBM and to demonstrate its applicability, we first compare the results of the OBM to those obtained from a series of simulations of the Atlanta metropolitan area using the Urban Airshed Model (UAM), a three-dimensional Eulerian grid model. The OBM is then used to analyze a dataset obtained from the 1990 Atlanta Ozone Study, an EPA field sampling program conducted during the summer of 1990. Because of limitations and potential flaws in the 1990 Atlanta dataset, the results of this OBM analysis are largely illustrative rather than definitive. Nevertheless, a few important issues are elucidated by the analysis. These include (1) the importance of accounting for biogenic hydrocarbons produced from urban vegetation; (2) the potential flaw in using early-morning VOC-to-NOx ratios to infer whether ozone production is limited by VOC or NOx; (3) the critical need for high-sensitivity nitrogen oxide measurements to quantify the sub-ppbv concentrations of NO during the afternoon hours; and (4) the need to consider a number of individual ozone episodes in studying an urban atmosphere because of the possibility that the degree of VOC- and NOx-limitation may vary from one episode to another.     

Design of A Large Scale Exposure and Sampling Facility for Street Level Auto Exhaust Emissions

A unique air handling facility was designed to introduce up to 12,000 cfm of street level air into laminar flow animal exposure chambers in an unaltered state except for the heating and cooling necessary in extreme weather to provide the animals with an habitable climate. The facility was built to determine the possible effect of street level exhaust emissions on the health of the general population. Another objective was to determine, by means of direct reading and recording instruments, the concentration of contaminants such as carbon monoxide, carbon dioxide, aerosols, nitrogen oxides, total oxidant, and unburned hydrocarbons.     

The Effect of Water Vapor on Ozone Synthesis in the Photo-oxidation of Alpha-pinene

A study of the effect of water vapor on the photochemical system NO₂ + alphapinene + hv was conducted. A Hotpack Environmental Room was used as a constant temperature chamber, a bank of ultraviolet and fluorescent lamps as a source of simulated solar radiation, and a 150-liter FEP Teflon bag as a reaction vessel. Representative concentrations of 10 pphm NO₂ and 50 pphm alphapinene were used in a 3 × 2 × 2 factorial design where absolute humidities of 0.0000, 0.0090, 0.01 80 g H₂O/g dry air were varied.

Matheson zero air was passed through a clean air train and used as the diluent. Nitrogen dioxide was added to the reaction mixture by a permeation tube, and water and alpha-pinene by evaporation techniques.

Variables measured as a function of time over a 2-hour irradiation period were total oxidants (Mast Ozone Meter), condensation nuclei (General Electric Small Particle Detector), ozone (Regener Chemiluminescent Ozone Meter), nitrogen dioxide and nitric oxide (Technicon Autoanalyzer), and alpha-pinene (Perkin- Elmer Model 800 gas chromatograph).

Upon irradiation, systems containing nitrogen dioxide and alpha-pinene formed oxidants, ozone, condensation nuclei, and nitric oxide. Based on the differences between simultaneous oxidant and ozone measurements, the formation of peroxide- like compounds may be inferred. During the course of the irradiation, nitrogen dioxide and alpha-pinene were consumed. The concentration-time profiles of all variables were characteristic of those exhibited by typical photochemical smog systems.

An effect of water vapor on the systems studied was demonstrated. Increasing humidity decreased net mean/time oxidant and ozone production and net maximum condensation nuclei production. These effects were significant at a 0.05 confidence level. Effects of water on average mean/time NO₂, NO, and alphapinene concentrations were insignificant at this level. The oxidant to ozone ratio was found to decrease with increasing humidity.

The significant decreases in net oxidant and ozone production and NO₂ consumption with increasing water vapor concentration in systems of nitrogen dioxide alone, suggests that water manifests an effect on pertinent inorganic reactions, and the data also suggest additional water participation in the organic reactions.     

Solubilization of PAH mixtures by three different anionic surfactants

Solubilization of naphthalene and phenanthrene into the micelles formed by three different anionic surfactants was investigated for single, binary, and ternary mixtures including pyrene. The three surfactants were sodium dodecylbenzene sulfonate (SDDBS), monoalkylated disulfonated diphenyl oxide (MADS-C12), and dialkylated disulfonated diphenyl oxide (DADS-C12). The order of increasing solubility enhancement of naphthalene and phenanthrene was SDDBS < MADS-C12 < < DADS-C12, which indicates that the hydrophobic chains in micellar core play more important role for the solubilization of polycyclic aromatic hydrocarbons (PAHs) than the benzene rings in palisade layer of a micelle. The solubility enhancement of naphthalene was slightly changed in PAH mixtures. The solubility of phenanthrene was greatly enhanced in presence of naphthalene but reduced in presence of pyrene. The explanation for these results could be that less hydrophobic compounds can be solubilized at the interfacial region of a hydrophobic core, which reduces the interfacial tension between the core and water, and then the reduced interfacial tension can support a larger core volume for the same interfacial energy.     

Outdoor-Indoor Levels of Six Air Pollutants

Comparisons were made of the levels of six air pollutants—total oxidant, per-oxyacetyl nitrate (PAN), nitric oxide, nitrogen dioxide, carbon monoxide, and particulate matter—outside and inside 11 buildings in the South Coast Basin of California during summer and fall.

Total oxidant levels inside depend upon how much outside air is being brought in and the residence time in the structure. With rapid intake and circulation, levels inside may be two-thirds those outside. With little intake and slow circulation, amounts inside decay to near zero. PAN is more persistent in buildings because it is more stable than ozone but also decays to low levels over an extended period. Oxides of nitrogen and CO are much more stable than oxidant or PAN and when carried into buildings remain until diluted or exhausted.

Particulate matter levels indoors depend largely upon velocity of air movement. Indoor areas where foot traffic was light or which had low ventilation rates had reduced amounts of particulate. Electrostatic precipitators were much more effective than coarse primary filters used in many buildings for removing particulate matter.     

Fingerprinting of Gasoline and Coal Tar NAPL Volatile Hydrocarbons Dissolved in Groundwater

Accidental spills and chronic leaks of fuel oil or other hydrocarbon material (e.g., coal tar) often result in subsurface accumulation of nonaqueous phase liquid (NAPL), which can be a subsequent source of contamination in groundwater. Linking hydrocarbons in groundwater to a source NAPL has been difficult when using standard target analytes (e.g., BTEX) because of differences in partitioning properties of the analytes between the source NAPL and groundwater. Because aqueous solubility is predicted to be the controlling influence in the partitioning of hydrocarbons from NAPL to groundwater, a solubility-based approach to matching dissolved hydrocarbons in groundwater to their source NAPL has been developed and validated for two sites with commonly encountered types of NAPL contamination. Specifically, a gasoline LNAPL and a coal tar DNAPL from two separate sites (West Virginia and California) and groundwater interfaced with these NAPLs were analyzed for approximately 50 gasoline-range hydrocarbons consisting of paraffin, isoparaffin, (mono-) aromatic, naphthene, and olefin compounds (PIANO). Solubility characteristics of selected alkyl aromatic hydrocarbons from the PIANO analysis were used to identify a set of diagnostic hydrocarbons, expressed as hydrocarbon ratios, which were found to be useful in distinguishing the source(s) of hydrocarbons in groundwater. At the West Virginia site, the diagnostic ratios in a downgradient groundwater sample were similar to those of a gasoline NAPL at that site, indicating the source of hydrocarbons to the groundwater was the upgradient gasoline NAPL. The diagnostic ratios of the groundwater in contact with the gasoline NAPL and the remote groundwater were also similar, providing evidence that the diagnostic ratios were retained during transport in the aquifer. At the California site, diagnostic ratios in a cross-gradient groundwater sample differed from those of the coal tar NAPL at that site, indicating that the remote groundwater hydrocarbons did not originate from the coal tar contamination. Environmental factors such as selective degradation of specific isomers and various geological conditions (e.g., soil mineralogy, and organic content) may confound the application of this solubility-based fingerprinting approach. Thus, it is recommended that multiple diagnostic pairs be simultaneously evaluated when considering this fingerprinting approach for specific sites and product types.     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.