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.     

Interpretation of Meteorological Pollutant Roses in Areas Subject to Nocturnal Drainage Winds

The composition of aerosol particle products formed from the photochemical reaction of terpenes with NO_x and the chemical reaction of terpenes with ozone was determined using direct insertion probe/high resolution mass spectrometry. Samples of the aerosol particles generated from these gas phase reactions were collected on stainless steel disks using a specially-designed impactor. The samples were analyzed using computer-controlled high resolution mass spectrometry. The photochemical reaction of limonene with NO_x produced more than 30 reaction products in the aerosol phase. The major products identified included aldehydes, alcohols, acids, peroxides, and nitrate esters of alcohols, acids, and peroxides. In addition, there was evidence of dimeric and possibly trimeric reaction products. The composition of aerosol particle products formed from the dark reaction of ozone with limonene was determined and found similar to those products generated in the photochemical reaction, excluding the nitrated species. Aerosol concentrations were monitored using nephelometry which indicated a conversion of terpene to aerosol of 50% or greater for both the limonene and terpinolene reaction systems. The results show that direct insertion probe high resolution mass spectrometric technique has the capability for determining the composition of very polar and high molecular weight materials in aerosol particles. The composition of terpene aerosol particle products and the mass spectral data obtained from their analysis can be used in further studies to determine the importance of terpene aerosol particle formation in ambient air.     

The Nationwide Program for Maintenance of Air Quality

The initial state implementation plans concentrated on attainment of the ambient air quality standards in the relatively polluted areas of the country. Many of these plans must now be modified to ensure that the ambient standards will be maintained for the foreseeable future, and to ensure that significant deterioration of air quality in clean areas of the country is prevented.

The existing implementation plans currently contain many measures which are applicable to the maintenance and deterioration efforts, but additional measures must also be developed. Many of these additional measures will involve future planning activities—most common of which will be land use planning activities.

The point is made that, after existing sources have reduced their emissions to the lowest practical level, further air pollution control can only be accomplished by implementing rational planning procedures for management of any new sources of air pollution. This will require extensive cooperation among the air pollution control community; regional, state, and local planning agencies; state and local governments; and the general public in order to ensure that future land use plans include appropriate air quality considerations.     

Emissions from Slash Burning and the Influence of Flame Retardant Chemicals

Pollutants sampled during the burning of 30 lb ponderosa pine fuel beds yielded emission factors for CO, hydrocarbon gases, and par-ticulate matter of 146, 8.4, and 9.1 lb/ton of fuel, respectively. When similar beds were treated with diammonium phosphate flame retardant, these factors increased to 166, 11.7, and 19.3 lb/ton of fuel, respectively.

Gas chromatographic analysis of hydrocarbon gases showed that 15-40% of this material was composed of methane and eth-ylene. Ethane and acetylene were the next most abundant materials, with photochemically important materials constituting minor portions of this gaseous component. Fuel beds treated with flame retardant produced more oiefins, and this production lasted throughout the smoldering phase of burning.

These tests showed that the smoldering phase of combustion is of major importance to air pollutant production during slash burning. The initial 80% of the fuel burned accounted for only 20-30% of HC and CO emissions. This suggests that a rapid mop-up of slash burns could substantially reduce air pollutant production.     

The Fate of Vanadium in an Urban Air Shed: The Lower Delaware River Valley

Vanadium compounds are toxic pollutants which require engineering control in the design stage. In the lower Delaware River Valley, the main sources are presently the combustion of vanadium rich fuel oils and the catalytic processing of high vanadium crudes. These and other Industrial emissions, result in atmospheric vanadium concentrations which have varied from 0.133 μg/m³ to 0.557 μg/m³ between 1958 and 1969. Compounds of vanadium, principally with oxygen and sulfur, are considered. The dominance of oxygen compounds over sulfur compounds as derived from equilibrium data, and the tendency of vanadium oxides to move toward vanadium’s maximum valence of +5, indicate the prevalence of V₂0₅ as the emission compound.     

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.     

Status and Problems of Regenerable Flue Gas Desulfurization Processes

Fourteen sulfur and/or sulfuric acid producing regenerate FGD processes were discussed at the 1974 FGD Symposium in Atlanta. During the period elapsed since then, considerable status change has occurred on many of these regenerable processes. Other regenerable processes which were not as well known during 1974 have surfaced in 1975. The problems of obtaining reducing gases (hydrogen sulfide, carbon monoxide, and hydrogen) for the reduction of sulfur dioxide product streams to elemental sulfur have become severe due to shortages of natural gas or other petroleum based feedstock. A new sulfur producing process which employs CO and H₂ directly (rather than the H₂S required for liquid and vapor base Claus reactions) is gaining attention. This paper discusses briefly: (1) the announced status of the many regenerable FGD processes, (2) the problem of reductant gas supply, and (3) the effect on FGD processes of using coal based reducing gas instead of reformed natural gas.     

AISI-EPA-Battelle Coke Oven Door Sealing Program

The problem of coke oven door leakage is generally recognized as one for which no proven solution exists. In 1974 the United States Environmental Protection Agency and the American Iron and Steel Institute entered into a jointly funded research project with Battelle Columbus Laboratories. The initial project was to define the problem by literature search, operator interviews and profile measurements of jambs and doors.

Numerous concepts of seal designs were developed and then rated by industry and Battelle reviews. It was determined that a metal-to-metal seal offered the greatest probability of success. It was felt that jamb warpage was the most serious problem to be solved.

In the fall of 1976 another contract was signed by EPA and AISI assigning Battelle the task of developing to the point of fabrication a system to eliminate or significantly reduce leakage from coke oven end closures. This program included mathematical modeling, physical modeling, field data collecting, analysis, and full scale unit design.

A retrofittable door seal design has been developed and preparations are underway for operating evaluation at eight steel plants. The design is retrofittable to the two principal coke oven doors in service and should accommodate the worst jamb warpage usually found.     

Sensitivity Studies of the Effects of Model Formulation on the Evaluation of Control Strategies for Photochemical Air Pollution Formation in the United Kingdom

In the OZIPP (ozone isopleth plotting package, developed by United States Environmental Protection Agency) a number of model specific assumptions with respect to chemical and physical processes are made. These assumptions are introduced into an alternative model developed at AERE Harwell, United Kingdom, in which a detailed chemistry and mixture of organic emissions is included. The impact on the AERE Harwell model results of the assumptions made in OZIPP of omitting ground removal of ozone (O₃) and peroxyacetylnitrate (PAN) and of employing an incomplete PAN chemistry and adopting a reaction rate coefficient of the key reaction NO + HO₂ → NO₂ + OH which is a factor 10 lower than the accepted value, are discussed. The composition of the organic emissions is an important model parameter, and it is shown how grouping of nonmethane hydrocarbon (NMHC) emissions into a small group of NMHC thought to be representative, often implies that O₃ and other pollutants are overestimated. The O₃ isopleth diagram for London constructed using the AERE Harwell model gives a somewhat different picture from that obtained with OZIPP. OZIPP in general predicts that NO_x control or combined hydrocarbon(HC) and NO_x control is efficient with respect to O₃ reduction whilst the AERE Harwell model predicts that HC control alone usually is more efficient than combined HC and NO_x control. Furthermore NO_x control alone may often increase the O₃ burden downwind in the AERE Harwell model.