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 Samples of the flow prior to and after its photoactivation were withdrawn either by an Aerosol Spectrometer (AS) or by a Royco Aerosol Photometer (PH).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.     

Apparent Photosynthesis as a Measure of Air Pollution Damage

A system has been developed to automatically measure the effects of air pollutants in the ambient air on the rate of CO₂ exchange by intact leaves of citrus trees growing in the field. A miniaturized system utilizing the same nondispersive infrared CO₂ analyzer has been designed to study individually the effects of different concentrations of air pollutants on photosynthesis and respiration by plants.     

Polynuclear Aromatic Hydrocarbons Associated with Particulates in Pittsburgh Air

Pittsburgh air was sampled continuously at one site for 886 hrs./sample at 45 cfm with a high volume sampler equipped with a horizontal elutriator as a first stage of separation, and an MSA 1106B glass fiber filter as a final particulate collection stage. The horizontal elutriator was designed to simulate the particulate deposition characteristics of the human respiratory tract. Samples were collected during the period June 1964 to February 1965. Respirable and non-respirable particulate samples were analyzed for polynuclear aromatic hydrocarbon content by a new technique which utilized dual column, flame ionization gas chromatography. It was possible to quantitatively analyze a concentrated benzene extract of the particulate sample for the following individual components: 1, 2 benzanthracene; chrysene; pyrene; 3,4 benzofloranthene; 1, 12 benzoperylene. It was not possible to distinguish between 3,4 benzopyrene, 1,2 benzopyrene and perylene; only the total quantity of these compounds present was detected. This analytical technique is comparable in sensitivity to formerly reported, more time-consuming methods and is very rapid, requiring less than one hour to perform after benzene extraction. Amounts of the above compounds associated with the two particulate fractions collected are reported and discussed.     

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.     

The Removal of Particulate Matter from Fluid Bed Catalytic Cracking Unit Stack Gases

The application of a high-efficiency centrifugal type of separator to fluid bed catalytic cracking units is described in which most of the catalyst particles often lost to the atmosphere are concentrated into a small part of the stack gas (2%). A further separation can then be made on this small stream by an auxiliary separator which further concentrates the catalyst particle into 0.1% of the initia stream. Performance of the main and auxiliary separators are such as to reduce the loss of catalyst particles in the stack gas from 800 ppm to less than 60 ppm in a typical unit. Large amounts of power can be recovered by application of expander turbines to catalytic cracking plants employing this system of separation.