Noncatalytic Auto Exhaust Combustor

Present methods for the determination of carbon monoxide are discussed including indicator tubes, the iodine pentoxide reaction and measurement by gas chromatography. In the gas chromatographic method an air sample is separated on a gas-solid chromatogra-phic column and the separated CO is converted to methane by hydrogenation at elevated temperature. The separated CO, in the form of methane, is passed into a hydrogen flame detector and measured. The conversion from CO to methane allows the use of a sensitive ionization detector in place of the thermal conductivity cell which is insufficiently sensitive for the measurement of trace amounts of CO. The optimum operating conditions are discussed. It is possible to determine one ppm CO in air. The iodine pentoxide reaction with CO has been combined with electrometric measurement. The iodine liberated is passed into a Ditte cell and the current generated is measured by an electrometerrecorder combination. This method is continuously direct reading with a permanent record. It is suitable for the continuous routine analysis of one ppm CO.     

Procedures in Sampling and Handling Auto Exhaust

Both the composition and discharge rate of auto exhausts vary widely and rapidly as speed and load demands upon the engine are changed. Moreover, among the combustion products are compounds that are highly reactive under proper conditions and others that are readily bound by receptive surfaces or absorbents. Under these conditions both the sampling procedure and subsequent sample handling must be such that (1) the sample that is recovered contains all or a fixed proportion of each incremental volume of the total to be represented and (2) the products so sampled are not allowed either to react with each other or to be lost or diminished in sample storage or transfer. Experimental research and development relevant to each requirement have been carried out, and results are reported and discussed. Two methods have been used for recovering sample-volume samples representative of the total volume produced during any combination of steady or transient engine modes. One employs a servo-followup system appropriately coupled to both the engine air-intake and to the sampling element; the sampling rate is continuously controlled to bear at all times a fixed ratio to the engine air-intake rate. The second method employs variable dilution, involving addition of diluent gas necessary to maintain a constant total of [exhaust + diluent]. If the mixture is sampled at a constant rate, the sample will contain exhaust appropriately proportioned. Experiments have shown differences in both hydrocarbon and NO_x values determined for comparable samples obtained by the two methods. The seriousness of this problem is discussed in relation to the sampling and sample handling procedures that are used.     

Determination of Nitrogen Oxides in Auto Exhaust

A new procedure for determining nitrogen oxides in automobile exhaust has been developed. The new procedure was included in a Bureau of Mines comparative study that aimed at evaluating various widely used methods for determining NO_x in auto exhaust. The methods included in the evaluation study follow: (1) Static oxidation in tank (ST method). The method involves oxidation of NO in residence with O₂ in a stainless steel tank. (2) Bureau of Mines method (BM method). The method involves application of the ST procedure in exhaust samples from which the hydrocarbons have been removed by combustion over catalyst. (3) Chevron Research method (CR method), as described in the literature. (4) Phenoldisulfonic acid method (PDS method), as described in the literature. The principal objective of this study was to generate experimental evidence which would lead to defining an optimum procedure for converting NO, present in exhaust gas, into NO₂; this conversion is desired so that the total of NO + NO₂ can be determined quantitatively in the form of NO₂. In pursuing this objective, the procedures prescribed by the foregoing methods were comparatively tested. The results indicated that all four methods are subject to error, the extent of which depends on the conditions employed. The BM method was superior from the standpoint of accuracy because it was less affected by interferences due to hydrocarbon-NO₂ reactions.     

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.     

Proportional Sampling System for the Collection of an Integrated Auto Exhaust Gas Sample

Carbon baking process involves evolution of fumes containing hydrocarbons and soot particles which cannot be discharged directly into the atmosphere. An incinerator can be used to clean these fumes. However, length of the baking cycle, nature of the fumes and variations in fume volume and temperature may result in excessive auxiliary fuel usage and inefficient incineration, if the incinerator is not designed properly. This paper describes the application of fundamental knowledge of aerodynamics, reaction kinetics and combustion, together with clear understanding of the process, in design of a highly efficient, fully automated incinerator. The design incorporates a unique but simple control system which results in reduction of auxiliary fuel usage without endangering the safety and efficiency of the incineration process. Operations and economics of the incinerator are described by illustrating a typical baking cycle and comparing actual fuel usage with the thermal ratings of the incinerator. Operating experience from a number of installations in the U. S. and Canada is also noted.     

Design of A Large Scale Exposure and Sampling Facility for Street Level Auto Exhaust Emissions

A unique air handling facility was designed to introduce up to 12,000 cfm of street level air into laminar flow animal exposure chambers in an unaltered state except for the heating and cooling necessary in extreme weather to provide the animals with an habitable climate. The facility was built to determine the possible effect of street level exhaust emissions on the health of the general population. Another objective was to determine, by means of direct reading and recording instruments, the concentration of contaminants such as carbon monoxide, carbon dioxide, aerosols, nitrogen oxides, total oxidant, and unburned hydrocarbons.     

Benzene accumulation in horticultural crops

In this study apple, blackberry and cucumber crops were exposed to elevated levels of benzene under controlled conditions. Benzene was retained in fruits of all crops, but only accumulated in leaves of blackberries and apples. The retention by cucumber fruits is suggested to result from the longer pathway for the desorption of benzene as a consequence of their increased tissue depth compared to leaves. The process of accumulation in blackberry and apple leaves is unknown. The ingestion of benzene via the food-chain pathway on the basis of this study is concluded not to be significant.     

Benzene exposure in Helsinki,Finland

Personal exposures and microenvironmental concentrations of benzene were measured in the residential indoor, residential outdoor and workplace environments for 201 participants in Helsinki, Finland, as a component of the EXPOLIS-Helsinki study. Median benzene personal exposures were 2.47 (arithmetic standard deviation (ASD)=1.62) μg m⁻³ for non-smokers, 2.89 (ASD=3.26) μg m⁻³ for those exposed to environmental tobacco smoke in any microenvironment and 3.08 (ASD=10.04) μg m⁻³ for active smokers. Median residential indoor benzene concentrations were 3.14 (ASD=1.51) μg m⁻³ and 1.87 (ASD=1.93) μg m⁻³ for environments with and without tobacco smoke, respectively. Median residential outdoor benzene concentrations were 1.51 (ASD=1.11) μg m⁻³ and median workplace benzene concentrations were 3.58 (ASD=1.96) μg m⁻³ and 2.13 (ASD=1.49) μg m⁻³ for environments with and without tobacco smoke, respectively. Multiple step-wise regression identified indoor benzene concentrations as the strongest predictor for personal benzene exposures of those not exposed to tobacco smoke, followed sequentially by time spent in a car, time in the indoor environment, indoor workplace concentrations and time in the home workshop. Relationships between indoor and outdoor microenvironment concentrations and personal exposures showed considerable variation between seasons, due to differences in ventilation patterns of homes in these northern latitudes. Automobile use-related activities were significantly associated with elevated benzene levels in personal and indoor measurements when tobacco smoke was not present, which demonstrates the importance of personal measurements in the assessment of exposure to benzene.     

California Vehicle Exhaust Control

The purpose of this paper is to relate California’s experience with vehicle exhaust controls for three model years and to discuss future possibilities for improving the continued effectiveness of these controls. Tests of exhaust controls on 1966 and subsequent model cars in public use indicate a reduction in hydrocarbons of about 60% for the vehicle life of 100,000 miles compared to uncontrolled cars. However, emission levels and emission deterioration rates in public use are higher than those reported from proving ground tests. Significant percentages of new cars are delivered from the factory maladjusted which has a significant effect on emissions. These maladjustments are worsened by automotive service personnel.     

Automobile Exhaust Control Devices

Irritant gases in concentrations that occur in polluted atmospheres might play a role in the degranulation and histamine release processes of mast cells in lung tissue. To test this hypothesis, young rats weighing 140-150 g were exposed to 1 ppm nitrogen dioxide for 2 hr. One group was killed immediately, and another group 24-27 hr after exposure. A third group was exposed to 0.5 ppm nitrogen dioxide for 4 hr and killed immediately. Animals serving as controls were placed for 1 hr into the exposure chamber ventilated with ambient air. Standard histological preparations were made after Carnoy’s fixative and subsequent staining with toluidine blue. The mast cells of the control animals appeared relatively intact with no evidence of disorientation. The cells of the animals exposed to NO2 and sacrificed immediately revealed rupture and loss of cytoplasmic granules with some disorientation. These changes were observed in the pleura, bronchi, and surrounding tissue with the effects more marked in the mediastinum. The mast cells of exposed animals sacrificed about 24-27 hr after discontinuing the exposure showed in some cases a combination of ruptured and intact cells with a predominance of the latter, and in other cases could not be differentiated from the controls. These findings indicate that 24 hr or more are required to reverse the acute effects of NO2 inhalation. The toxicological implications will be discussed. The release of granular substances in the lung tissue when NO2 is inhaled signifies the onset of an acute inflammation.     

Oxygenates in Exhaust from Simple Hydrocarbon Fuels

Photochemical air pollution is known to be caused largely by automotive emissions such as hydrocarbons and oxygenated hydrocarbon derivatives. Unlike the hydrocarbons, the contribution of the oxygenates has been virtually unexplored, mainly because of lack of appropriate analytical methods. The objective of this study was to identify and estimate the levels of oxygenated hydrocarbon derivatives in exhaust from simple hydrocarbon fuels. This information is expected to yield ultimately estimates of the relative levels of various classes of oxygenates in exhaust from full-boiling-range gasolines. Identification and measurement of oxygenates in exhaust from the simplified fuels were accomplished using gas chromatography in conjunction with time-of-flight mass spectrometry. The analytical procedure involved concentration of the exhaust organics, followed by a two-stage chromatographic separation of the resultant mixture of oxygenates and hydrocarbons. Identified oxygenates in exhaust from nine test fuels included saturated and unsaturated aldehydes, ketones, and alcohols, as well as ethers, esters, and nitroalkanes; analytical data on organic acids were inconclusive. Of the identified noncarbonyl oxygenates, phenols, cyclic ethers and nitromethane appear to be relatively the most abundant.     

Nature of Odor Components in Diesel Exhaust

Offensive exhaust odors are characteristic of diesel engines. One problem in control and reduction of odor is lack of understanding of odorant sources and mode of formation. The solution of this problem depends on identification of the odorants so that study of their formation and control can be undertaken. A human panel performed odor assessments in studying raw and modified diesel exhaust and synthetic blends representing portions of diesel exhaust. Their assessments were used in determining odorant identity and quantitative contribution to exhaust odor. Low molecular weight aldehydes appear to contribute little to diesel odors. The sulfur and nitrogen oxides have been examined as odorants but of these apparently only nitrogen dioxide is a potential odor contributor.