The Effect of Nucleating Particulates on Photochemical Aerosol Formation

The role of nucleating particulates in the formation of photochemical aerosols has been studied in a steady, laminar flow of ultrafiltered air containing NO₂ and octene-1 in the concentration range of (30 to 170 ppm) when subjected to intense irradiation under isothermal conditions. The particulates consisted of monodisperse polystyrene latex (d = 0.36 μ.) in concentrations similar to those in the atmosphere (6 × 10¹ to 3 × 10³ cm^–3); the irradiation intensity varied between (6 to 40 × 10³ lumen/liter) and the mean exposure duration between 30 and 180 sec. Samples of the flow prior to and after its photoactivation were withdrawn either by an Aerosol Spectrometer (AS) or by a Royco Aerosol Photometer (PH). While these indications refer thus to the same system, they differ, because the photometric data include all colloidal components in the airborne state, whereas the counts obtained from the AS deposits refer only to the nucleated latex particles. The following pattern becomes evident: The photochemical reaction yields fractional products (less than three percent) which have the tendency to agglomerate (or polymerize) due to their relatively low volatility—independent of the presence or absence of nucleating particulates. In their presence, this reaction becomes kinetically more probable and thus faster, hence the accumulant formation occurs preferably on the nuclei and causes their growth such that, e.g., a 10-fold higher nuclei concentration will produce under the same conditions 10 times the accumulant mass while autonucleation is suppressed. The growth process appears thus principally different from that of fog formation by H₂O-condensation, whereas for identical super saturation it is inversely proportional to the nuclear concentration. In the absence of nuclei autonucleation, i.e., self-agglomeration, occurs at a much lesser reaction rate and higher photon demand. The growth rate of the nuclei, when present, depends on the concentration of the oxidation catalyst (NO₂), its interaction with the nuclei surface is indicated. Under identical conditions the mass of nuclear accumulant is directly proportional to the concentration of the reactive hydrocarbon, while the growth rate depends on the light intensity and the exposure duration. The findings indicate that density and nature of particulate matter present in an air mass prior or during photo-activation are—aside from the chemical reactant levels—of major significance in aerosol formation.     

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.     

Pennsylvania’s Compuiterized Air Monitoring System

The Pennsylvania Air Pollution Commission has developed a regulatory program based upon the control of local air pollution problems and reduction of pollutant levels in air basins. The geographical boundaries of 10 air basins have been established. The Commission’s air basin regulations will provide for the reduction of over-all pollutant levels and for emergency procedures in the event of adverse meteorological conditions. The paper discusses the format and objectives of the program.

In order to effectively enforce the air basin regulations and maintain the necessary surveillance of the state’s air quality, a "computerized real time on-line integrated air monitoring-data handling system" has been designed. The system will incorporate a network to constantly monitor the air in each air basin.The primary objectives of the system are: 1. Constant surveillance of air pollution in the air basins.

2. Provide information on air pollution potential alerts.

3. Aid in further development of air quality criteria and regulations.

The air monitoring network is estimated to include approximately 25 remote stations. Each remote will contain air pollution and meteorological sampling equipment and hardware to telemeter to a central station. The data will be transmitted over leased telephone lines. The central station in Harrisburg will contain the necessary hardware to receive and process data, calculate and display results and permit supervisory control of the network. Output options will include immediate display of edited data, command and alarm information, and presentation of statistical results.

Although the air monitoring system is one of the principle ingredients of the program, the air basin concept encompasses other component systems designed to knit together the entire air pollution control program in Pennsylvania.     

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.