Determination of the Detailed Hydrocarbon Composition and Potential Atmospheric Reactivity of Full-Range Motor Gasolines

The quantitative data obtained with a capillary GLC method, which is used to determine the individual C₃-C₁₂ hydrocarbons in full-range motor gasolines, have been employed in a computer program to calculate the hydrocarbon composition of the vapor in equilibrium with a gasoline at 100°F, as well as the equilibrium vapor-pressure of the gasoline at that temperature. The method used for computation is similar to that previously described by McEwen, assuming the gasoline to behave as an ideal liquid. Also calculated is the potential atmospheric reactivity of this equilibrium vapor relative to that from other gasolines when specific reactivity weighting factors for the individual hydrocarbons are employed. Calculated total vapor-pressure data agree well with experimental Reid vapor-pressure data obtained for typical premium-grade gasolines. Definite differences were observed in the relative potential atmospheric reactivities calculated at 100°F for the equilibrium vapors from the test gasolines.     

Instrumenting Light Aircraft for Air Pollution Research

Light aircraft and helicopters have been occasionally used to conduct aerial traverses for a single pollutant or atmospheric tracer. The continuous analyzer or sample collector is temporarily tied down with a seat belt or hand held. Flight variables are visually observed and written on the recorder chart, a notebook or possibly voice-recorded on a portable tape recorder. The versatile airborne instrumentation package described can measure and record up to 27 pollutant and flight variables from a Cessna Skymaster center-line thrust, light twin. Real-time analysis instrumentation include non-dispersive infrared analyzers for CO₂, CO, and hydrocarbons, conductivity and coulometric analyzers for sulfur dioxide and sulfur-containing gases, and Charlson-Ahlquist visual range nephelometer. A Battelle “bulk sampler” is used to collect particulates for weighing and microscopic examination. Indicated air speed, altitude, rate of climb, magnetic heading, temperature, and relative humidity are continuously measured. All variables are sequentially recorded on a 7-track, 200 bit per second, 27-channel, magnetic tape data logging system. Measured variables are recorded once each 0.3 to 0.8 sec—equivalent to 33-100 ft of traversedepending upon the number of variables recorded (i.e., between 9 and 27) when flying at 90 mph. Tape data are reduced directly by IBM 360 computer to a digital print-out or from tape to an X-Y analog plot.     

Sulfur Dioxide Removal and Recovery from Pulp Mill Power Plants

The use of soda ash liquor to scrub SO₂ rich power plant flue gases was studied using an Airetron pilot scrubber with a maximum capacity of 3000 cfm. The relative effects of the major operating variables— temperature, soda ash concentration, and the gas/liquid flow ratio—on the absorption phenomenon were determined. Orthogonal factorial experiments were used to derive a response function relating mass transfer values to operating variables. The economics of a full scale NSSC installation are discussed.     

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.     

Evaluation of the Effectiveness of The Lead Peroxide Method for Atmospheric Monitoring of Sulfur Dioxide

This paper presents a simplified analysis to determine the variables that affect the empirical correlation factor used in the lead peroxide method. The rate of sulfation has been determined from two different models. In the first model, the mass transfer rate is calculated from the gas phase resistance alone whereas in the second model, the diffusion resistance in the gel phase is assumed to be the rate limiting step. Although the gas phase and the gel phase resistances may be both important in the actual case, it has been found that the correlation factor based on the first model is adequate to describe general experimental observations. Reasonable agreement has been obtained between the measured and the calculated va|ue of the correlation factor.     

Ethylene: An Urban Air Pollutant

Ethylene is an unusual air pollutant in that it is a plant hormone. Motor vehicle exhaust is a primary source. In the Washington, D. C, area, ethylene concentrations ranged from 700 ppb in the city center to 39 ppb in areas outside the circumferential beltway. Plants grown in these concentrations of ethylene, using controlled environment chambers, exhibited typical symptoms of ethylene toxicity: reduced growth, premature senescence, and reduced flowering and fruit production. When plants were grown in carbon-filtered ambient air, which was also filtered through KMnO₄ to remove ethylene by oxidation, growth, flowering, and fruit production increased. These observations demonstrate that ethylene air pollution is a continual source of stress for plant growth and development in an urban environment.