The Effect of Fuel Composition on Atmospheric Aerosol Due to Auto Exhaust

Aerosols attributable to automobile exhaust can be classified as two types—primary aerosol (initially present in the exhaust) and secondary aerosol (generated photochemically from hydrocarbons and nitrogen oxides in the exhaust). In this study, investigation was made of possible effects of motor-fuel composition on the formation of these aerosols. Secondary aerosol, of principal interest in this work, was produced by irradiating auto exhaust in Battelle-Columbus’ 610 ft³ environmental chamber. A limited number of determinations of primary aerosol in diluted auto exhaust was made at the exit of a 36 ft dilution runnel. Determination of both primary and secondary aerosol was based on light-scattering measurements.

Exhaust was generated with seven full-boiling motor gasolines, both leaded and nonleaded, in a 1967 Chevrolet which was not equipped with exhaust-emission control devices. Changes in fuel composition produced a maximum factor of three difference in light scattering due to primary aerosol. Aerosol yields, for consecutive driving cycles on the same fuel, vary considerably; as a result, ranking the fuels on the basis of average primary aerosol yield was not very meaningful. In addition to fuel composition, the more important independent variables are initial SO₂ concentration, relative humidity and initial hydrocarbon concentration. Statistical analysis of the data indicates that the seven test fuels can be divided into two arbitrary groups with regard to secondary aerosol-forming potential. The fuels in the lower light-scattering group had aromatic contents of 15 and 21%, while those in the higher light-scattering group had aromatic contents of 25, 48, and 55%. Although the fuels can be grouped on the basis of a compositional factor, the grouping of fuels with aromatic content ranging from 25 to 55% indicates that this compositional factor cannot be equated simply with aromatic content. In an associated study of the aerosol-forming potential of individual hydrocarbons prominent in auto exhaust, it was observed that aromatics produce substantially more photochemical aerosol than olefins and paraffins. However, experiments with binar/hydrocarbon mixtures containing aromatjcs, as well as in these exhaust experiments, a strong dependence of aerosol yield on the aromatic components is is not observed. Thus, the data indicate that the dependence of secondary aerosol formation on fuel factors is a complex one and cannot be predicted solely on the basis of a sirigle hydrocarbon component reactivity scale.

The two types of automobile aerosol did not have the same dependence on fuel, composition. The variation in total light scattering attributable to primary plus secondary aerosol was less than that due to either component alone. It therefore was concluded that the light scattering due to automobile exhaust emissions in these experiments was not significantly affected by changing fuel composition.     

On the Relation Between the Indoor and Outdoor Concentrations of Nitrogen Oxides

Simultaneous measurements were made of the concentrations of NO, NO₂, and CO inside and outside of a building. The building is located in the Los Angeles area, which is heavily polluted by photochemical smog, and the experiments were conducted at a time of the year when the pollutants in question tend to be high. The results shows that there is a direct relationship between the inside and outside concentrations, and that the phase lag between the concentrations depends principally on the ratio of the building volume to the ventilation rate. Although the outside concentrations of the pollutants in question did not follow the same pattern every day, peak concentrations seemed to be related to “rush-hour” traffic. By reducing ventilation rates during these periods, it may be possible to reduce the concentration peaks inside of the building. The building involved in the current study was not located in the immediate vicinity of heavy traffic, and the indoor concentrations of NO, NO₂, and CO did not appear to be very severe when compared to those defined by present air quality standards. Finally, the results support the belief that NO and O₃ do not co-exist indoors except in very small quantities.     

The Inhibition of Photochemical Smog

Additional inhibitors for the conversion of NO to NO₂ in C3H6—NO—0₂ irradiated mixtures have been tested at 25°C. These mixtures initially contained 16 mTorr C₃H₆, 8 mTorr NO, 0.012 mTorr NO₂, additive, and enough O₂ to bring the total pressure to 100 Torr. The NO₂ pressure was monitored photometrically. In the absence of additive, the NO₂ pressure first increases with irradiation time reaching a maximum conversion at about 15 minutes. As the irradiation time increases beyond 15 min, the NO₂ pressure drops. Before adding the inhibitors, runs were done with 10 Torr of CO added, and in these runs the conversion was speeded so that the maximum in NO₂ pressure occurred at 10 min. This enhancement in conversion rate is considered to be diagnostic for the presence of HO radicals. Next 10-min irradiations were done with various amounts of hexafluorobenzene (C₆F₆), nitrobenzene (C₆H₅NO₂), or naphtha lene (C₁₀H₈) added. The NO₂ pressure was reduced to one-half its value in the absence of inhibitor with 270 mTorr C₆F₆’, 220 mTorr C₆H₅N0₂, or 4 mTorr C₁₀Hg. The C₁₀H₈ is a very efficient inhibitor, but additions of up to 1 8.5 mTorr C₁₀H₈ did not reduce the N0₂ pressure to zero. Studies of the percent conversion of NO to NO₂ vs. irradiation time were done with either 4.2 mTorr C₁₀H₈ or 40 mTorr 2,6-di-ferf-butyl-4-methylphenol (Ph) added. In the former case the peak conversion was delayed from 15 to 22 min, while in the latter case no delay occurred. However, with the Ph added, there appeared to be some reduction in the maximum value of percent conversion.     

Emission Control in Coking Operations By Use of Stage Charging

At the Clairton Coke Works of the United States Steel Corporation (the world’s largest coke plant), with coal charges of about 30,000 net tons per day, a system designated as “stage charging” has been developed for charging coal into the coke oven chamber without emissions to the atmosphere. The principles of the system are based on controlled sequential flow of the coal from the charging hoppers, during which the oven chamber is maintained under a very slight negative pressure condition by use of steam aspiration in the offtakes for on-the-main charging. The techniques are basic but require knowledge of the coal characteristics, adequate and properly maintained aspirating systems, including clean offtake piping, control of coal volume in the individual hoppers, and last, and probably most important, adherence by the operating crew to specific charging and leveling practices.     

Results of Field Measurements of Industrial Particulate Sources and Electrostatic Precipitator Performance

This paper presents results of source size distribution measurements over the size range from 0.1 μm to 5 μm for six classes of particulate sources and fractional efficiency measurements on five full scale electrostatic precipitators and one pilot scale precipitator. The precipitators all showed moderately high to high particulate collection efficiencies for particles having diameters larger than a few micrometers or smaller than a few hundredths of a micrometer and a minimum in collection efficiency for particles having diameters of a few tenths of a micrometer.     

Calculation of the Charging Rate of Fine Particles by Unipolar Ions

Theories of particle charging based on boundary value solutions to the diffysional equation may not be applicable to electrostatic precipitators where the ion density is rarely more than an order of magnitude greafer than the particle concentration. A new charging equation, based on kinetic theory, is presented which evaluates the charging rate in terms of the probability of collisions between the flust particles and ions. In the presence of an external electric field, the surface of the particle is divided into three charging regions, and separate charging rates are calculated for each region. The total charging rate is the sum of these three individual rates. For large particles and high electric fields, this theory predicts essentially the same charging rate as the classical field charging equation of Rohmann and Pauthenier. For low electric fields, the theory reduces to White’s diffusional charging equation. Agreement is within 25% of Hewitt’s experimental results over the entire range of variables where data are available. For practical charging times, agreement is within 15%.     

Improvement of Ambient Sulfur Dioxide Concentrations by Conversion from Low to High Stacks

A study of the “before” and “after” ground-level S0₂ concentrations near the Muskingum River Plant of the American Electric Power System shows that the conversion from low to high stacks has accomplished marked reductions in ambient concentrations. These reductions are in reasonable agreement with theoretical calculations and are most apparent within 5 km of the source. EPA Standards are now being met in this area despite the presence of the 1440 MW power plant burning 5% sulfur fuel with no treatment of the stack gas.     

Stack Sampling of Hygroscopic Particulates In an Entrained Water Environment

Reference methods for the determination of mercury emissions from stationary sources typically include collection of mercury by solutions which are acidic and oxidizing. In the presence of high levels of SO₂ the oxidizing capacity of these absorbing solutions will be degraded and the collection efficiency for mercury compromised. This seriously limits the usefulness of the reference methods as they apply to the mining and smelting industries. In the present work peroxide is used to remove SO₂ and acidic permanganate is used to collect mercury. At a mean sampling rate of 10 L/min concentrations of at least 12 mg/m³ mercury can be satisfactorily collected in the presence of up to 20,000 ppm SO₂.     

Solid Absorbent Method for Sampling and Analysis of Nitrogen Dioxide in Ambient Air

A sampling and analysis system was developed for measuring concentrations of nitrogen dioxide in ambient air. Copper shot was found to be an effective absorbent for collecting samples at ambient levels. The analytical system was based on the desorption of the sample from the copper by heating in a hydrogen carrier stream. The desorbed sample was then determined by a combination of catalytic pyrolysis, which converted it to ammonia, and a Coulson Conductivity Detector. Data are presented showing overall recovery, effects of storage of collected samples, results for 24-hour sampling and interferences. Studies indicated the feasibility of the method for short time sampling as well as for 24-hour sampling periods. The detection limit was shown to be as little as 100 ng NO₂ in laboratory studies. This solid absorbent method provides a simple, convenient, and compact means for air sampling.     

Effect of Oxidizing and Reducing Conditions on the Reaction of Water with Sulfur Bearing Blast Furnace Slags

The evolution of H₂S and SO₂ from hot blast furnace slags by reaction with H₂O has been found to be dependent upon the presence of O₂ or H₂ in the reaction zone as well as on the temperature. H₂ has been found to produce a small increase in H₂S and a small decrease in SO₂ emission, while O₂ has been found to produce a very great inhibiting effect on H₂S emission and only a small increase in SO₂ emission. The total emission of sulfur bearing gases is much less when H₂O + air is blown at the slag than when H₂O + Ar is blown at the slag, particularly at 1200°C and above. These effects may be useful in attempts to design systems for slag quenching which will produce less pollution.