The Analysis of Airborne Sulfate

This report reviews the current state of analytical methodology for sulfate in airborne particles. Methods for determination of total aerosol sulfate and total soluble sulfate are assessed. A more detailed review of the relatively new techniques for quantitative speciation of airborne sulfate then follows. Size distribution methodology and filter sampling difficulties relating to the collection of airborne sulfate-containing particles are enumerated. Experiments are suggested which use new, improved, and potentially applicable sulfate speciation techniques to obtain a better understanding of the generation, transport, transformation and removal processes that, in turn, determine the identity and concentrations of sulfate species in ambient air.     

Characterization of Particulates from Power Plants

The emphasis on participate control from industrial processes has been shifted recently towards fine particulates, having diameters less than 3 microns. There exists an urgent need for more scientific information of fine particle characterization.^1,2 Coal and oil fired power plants are among the largest anthropogenic point sources of particulate matter.³ Limited knowledge is available on particle size distribution and trace metal composition in power plant emissions.^4-7 The morphological properties of particle emissions have been largely neglected. In this report we present some information on particle characteristics for an oil-fired and coal-fired power plant.     

Biological Effects of Carbon Monoxide vs. Whole Emissions from Engine with Catalyst

The introduction of oxidizing catalytic converters in the exhaust system of automobiles has been found to be effective in reducing carbon monoxide, total hydrocarbons, and some other components of tailpipe emissions. The utilization of these converters, however, has also caused further oxidation of sulfur compounds producing an increased amount of sulfur trioxide (SO₃) which yields sulfuric acid and sulfates.¹ Studies on the biological effects of these sulfur compounds are in progress in our laboratory and preliminary findings are reported separately. This paper compares the biological effects of exposure to whole emissions from engines with and without converter and exposure to carbon monoxide alone.     

Turbulent Plume in a Turbulent Cross Flow: Comparison of Wind Tunnel Tests with Field Observations

Plume rise downwind of a large stationary gas turbine was measured in the field and the conditions were then scaled in the laboratory. For the laboratory, the plume exit conditions, wind velocity and temperature profiles, and wind direction were matched. It was found that for high temperature exhaust, the buoyancy is best matched by calculating a dimensionless density difference. With properly calculated buoyancy length scales, the plume trajectories were compared and were found to agree quite well. The probability distributions of the entrainment constant and the average values of the entrapment constant with downwind distance were compared. The field data showed about 15% greater plume rise. The median entrainment constant was about 10% greater for the lab test and the shape of the probability distribution matched very closely.     

Studies on the Effects of Saline Aerosols of Cooling Tower Origin on Plants

A research program was undertaken to develop information that could be used to estimate the risk of adverse effects of saline cooling tower drift on native and cultivated flora in the Indian Point, New York area. Eleven species of woody plants were exposed at 85 % relative humidity to a saline mist with 95% of the particles between 50 and 150 nm in diameter. Three biological factors—stage of development, species, and phenotype—determined the susceptibility of plants to saline aerosols when the occurrence of any lesion on the foliage was used as a measure of response. The effects of stage of development on the incidence and severity of foliar lesions depended upon the kind of plant. In deciduous woody species, the youngest leaves were most susceptible, but in conifers, the year-old needles were most susceptible. Canadian hemlock was the most susceptible species and witch hazel was the least susceptible. Median effective doses for these two species, although undetermined, could be more than 100-fold different (less than 2.4, the lowest used, and greater than 264 ng CI cm^-2, respectively). Other species, ranked in decreasing order of susceptibility were: white ash, white flowering dogwood, forsythia, chestnut oak, silk tree, black locust, red maple, eastern white pine, and golden rain free. Phenofypic variation within a species was not so great—within a 10 to 20-fold increase in dose the incidence of injury went from 0 to 100%. Exposures with bush bean showed that the relative humidity (RH) during or after the exposure period affected the incidence of saline induced foliar injury. A change from 50 to 85% RH doubled the effectiveness of the saline mist. It was also found that compared to particles between 50 and 150 jum in diameter, an increase in the fraction of particles above 150 /xm increased the toxicity of the mist.     

Distribution,Sources and Sinks of Atmospheric Halogenated Compounds

Based on two comprehensive field studies conducted in California, background concentration (parts per trillion) of N₂O (296.0 X 10³), SF₆ (0.16), CCI₂F₂ (180.8), CCI₃F (103.8), CCI₂FCCIF₂ (16.3), CCI₄ (114.2), CH₃CI (952.9), CHCI3 (23.4), CH₃I (2.4), CH3CCI3 (84.0), CCI₂CCI₂ (43.1), CHCICCI2 (14.5) and CH₃Br (—) have been reported. These trace constituents were identified using retention data on eight GC columns, their electron attachment properties, and their EC thermal response. All but CHCICCI₂ and CH₃Br were measurable 100% of the time at both sites. Cryogenic procedures for SF₆ ambient measurement were developed and successfully used. By an analysis of worldwide emissions of these trace constituents, their ambient levels, and their atmospheric lifetimes, it was possible to determine their origin (natural or anthropogenic). Our results indicate that 27% of organic chlorine contribution to the troposphere comes from fluorocarbons as opposed to a 73% contribution from the chloro-carbons. Further, the anthropogenic organic content in the troposphere was found to be about twice the natural content. Very high CHCI3 concentrations in onshore ocean waters were measured. Ambient data supporting the anthropogenic origin of CCI₄ have been presented.     

The Formation of Mg3Ca(S04)4 during the Sulfation Reaction of Dolomite

Abstract

Inspection and maintenance programs for motor vehicles in the United States increasingly use loaded mode mass emissions testing (IM240). A method was developed to predict mass emission rates and mass emission changes, particularly from repair benefits, using a low-cost, portable four-gas non-dispersive infrared (NDIR) vehicle exhaust gas analyzer. A single vehicle was tested several times with the analyzer while on the dynamometer and undergoing successive repairs. Excellent correlations for CO and HC were observed. Five vehicles were measured using an on-road driving loop before and after emissions-related repairs, while another three vehicles were tested with no repairs performed. The on-road concentration data used to guide the repair process were converted to grams per gallon; when divided by estimated miles per gallon, this gave grams per mile emissions for comparison to IM240. Correlation coefficients (r²) of 0.87 for CO and 0.76 for HC were achieved for the 13 tests. The linear correlations between IM240 and emissions measured by this method would allow repair facilities to perform a relatively inexpensive test for diagnostic purposes and to estimate repair effectiveness without the need for a dynamometer.     

Gas and Particle Emissions from Automobile Tires in Laboratory and Field Studies

This paper is directed to air pollution scientists interested in special mobile emission sources. The purpose was to determine the contribution which automobile tires make to air pollution. The gaseous hydrocarbon and sulfur compounds emitted in laboratory tests were identified. Although these hydrocarbons can participate in smog reactions, their mass emission rate is less than 0.1 % of the current exhaust hydrocarbon emission rate. Hydrocarbons from tires are not measurable near a freeway. The particulate emitted from tires ranges in size from 0.01 μm to more than 30 μm, with the larger particles dominating the total mass. Measurements along a California freeway showed that most of the tire debris had settled within 5 m of the pavement edge. Airborne rubber concentrations were less than 0.5 μg/m³, or less than 5% of the total tire wear. These field measurements confirm the indoor emission pattern and verify that tire wear products are not a significant air pollution problem.     

A Model for Uptake of Pollutants by Vegetation

A mass transfer approach is used in developing a practical mathematical model of gaseous pollutant uptake by leaves in which a series of resistances is summed across a concentration difference. The body of information presented in this paper is directed to plant pathologists or physiologists in the field of vegetal-pollutant effects and to people interested in the natural removal of air pollutants by vegetation. Correlations are given to calculate the aerodynamic and the stomatal resistances to uptake, while both a qualitative investigation and quantitative estimates are made of the mesophyllic resistance. The factors which control the aerodynamic resistance, r_a, are leaf size and wind speed, while the leaf physiology is the determinant of the stomatal resistance, r_s . It is noted that the chemical reaction rate and pollutant diffusivity in the mesophyll control the mesophyllic resistance, r_m, though the overall gas phase mesophyllic resistance, Hr_m, is strongly a function of pollutant solubility in water. Finally, the overall model is compared to earlier experimental work on vegetal uptake of SO₂.