A Movable Laboratory for Controlled Clinical Studies of Air Pollution Exposure

The cause of the Yokkaichi asthma episode (1960-1969) has been analyzed. It Is concluded that the respiratory diseases were due not to sulfur dioxide but to concentrated sulfuric acid mists emitted from stacks of calciners of a titanium oxide manufacturing plant located windward of the residential area.     

The Inadequacy of PSD Increments to Protect Visibility in Class I Areas

This study includes an application of the first two phases of a new three-phased decision-making structure that was developed to overcome the problems related to ecological safety and social justice in site selection applications. It was conducted on a current site selection problem related to the municipal solid waste disposal facilities in Kocaeli, the most industrialized region of Turkey. In order to assess the deficiencies of the legal site selection procedures related to ecological safety, two different decision tree modes were applied separately. The first mode (“Legislation”) concerns the current buffer zone applications given in the regulations, while the second one (“Proposed”) includes the applications of the new decision-making structure proposed in this study. Since it was assumed that the subjective tendencies of the decision makers on the weightings would have a significant effect on the final decision, these two modes were assessed by employing two different weighting models. The results were obtained from all of the scenarios related to selection of suitable sites with three different area requirements (15, 250, and 500 acres) for the solid wastes generated in the Kocaeli region. The results showed that the possible changes in the decision structure could cause significant differences in the final decision related to selection of the most suitable sites. The most highest and lowest differences were at the “Legislation” mode for 15 acres and 500 acres, respectively. Furthermore, the results obtained in the study showed that the possible differentiations in the criteria weightings could also cause significant differences in the suitability ranking. Therefore, to get a reliable final decision, a statistical assessment of these differentiations should be made.

Implications: The results showed that the possible changes in the decision structure could cause significant differences in the final decision related to selection of the most suitable sites. Furthermore, the results obtained in the study showed that the possible differentiations in the criteria weightings could also cause significant differences in the suitability ranking. Therefore, to get a reliable final decision, a statistical assessment of these differentiations should be made.     

Technical Session Preliminary Schedule Announced for 1988 APCA Annual Meeting

ABSTRACT

Stable heterogeneous catalysts for the oxidative removal of CO from air at ambient temperatures have been developed. An alumina support impregnated with PdCl₂, CuCl₂, and CuSO₄ is described. Optimal activity was obtained with Pd 0.020 mol/kg, Cu 0.50 mol/kg, CuCl₂ 20-30% of total Cu, a 2- to 24-hr soak, filtration of surplus raffinate, and a 2- to 4-hr firing in air at 200-350 °C. The catalysts are effective at 20-26 °C and relative humidities in the 15-90% range. They are reversibly deactivated by completely dry or water-saturated air streams. These catalysts have been tested at space velocities up to 30,000 hr^-1. In contact with <100 ppm CO, they are highly efficient, removing ~99% of the CO with contact times of ~120 msec (pseudo-first order k' > 25 sec^-1). At much higher CO concentrations, the maximum CO loading rate—limited by the Cu(I) reoxidation rate—is approximately 17 m mol CO per Limol Pd per hour.     

Evaluation of the Use of Solar Irradiation for the Decontamination of Soils Containing Wood Treating Wastes

Laboratory evaluation of the efficacy of soil phase photodegradation of recalcitrant hazardous organic components of wood treating wastes is described. The photodecomposition of anthracene, biphenyl, 9H-carbazole, m-cresol, dibenzofuran, fluorene, pentachlorophenol, phenanthrene, pyrene and quinoline under UV and visible light was monitored over a 50-day reaction period in three test soils. Methylene blue, riboflavin, hydrogen peroxide, peat moss and diethylamine soil amendments were evaluated as to their effect on the enhancement of compound photoreaction rates in the test soil systems. Dark control samples monitored over the entire study period were utilized to quantify non-photo mediated reaction losses. Compounds losses in both the dark control and irradiated samples were found to follow first order kinetics, allowing the calculation of first order photodegradation reaction rate constants for each test soil/compound combination. Degradation due to photochemical activity was observed for all test compounds, with compound photolytic half-lives ranging from 7 to approximately 180 days. None of the soil amendments were found to improve soil phase photodegradation, although photosensitization by anthracene was shown to significantly enhance the rate of photodegradation of the other test compounds. Soil type, and its characteristic of internal reflectance, proved to be the most significant factor affecting compound degradation rates suggesting the necessity for site specific assessments of soil phase photodegradation potential.     

Transportation-Related Volatile Hydrocarbon Source Profiles Measured in Atlanta

Abstract

Samples representative of transportation-related hydrocarbon emissions were collected as part of the 1990 Atlanta Ozone Precursor Monitoring Study. Motor vehicle emissions were sampled in canisters beside a roadway in a tunnel-like underpass during periods of heavy traffic. Airport and aircraft emissions were approximated by canister samples obtained at a major airport facility. Three octane grades of gasoline were purchased from six major vendors in Atlanta. Canister samples were prepared using these fuels to approximate the whole gasoline and gasoline vapor composition of the fuels in use during the study. All samples were analyzed by gas chromatography/flame ionization detection (GC/FID) for their hydrocarbon content. Detailed speciated hydrocarbon profiles were developed from this source sampling and analysis program for use in the Chemical Mass Balance (CMB) model. Profiles presented and discussed here represent the hydrocarbon composition of emissions from a roadway, composite headspace gasoline at two temperatures, composite whole gasoline, whole gasoline at three octane grades, and an airport. The roadway profile is compared with similar profiles in the literature, and recommendations are made regarding its use in the CMB model. The roadway and fuel profiles are discussed in the context of the MOBILE5 model outputs. The headspace gasoline vapor profile presented here is compared with a headspace gasoline vapor profile calculated from the whole gasoline profile by means of Raoult’s law. Agreement between the measured and calculated headspace profiles is excellent. The airport profile demonstrates the importance of high molecular weight volatile hydrocarbons in airport and aircraft emissions.     

Effectiveness of Smokeless Ashtrays

Abstract

Most environmental tobacco smoke (ETS) issues from the tips of smoldering cigarettes between puffs. Smokeless ashtrays are designed to reduce ETS exposure by removing particulate and/or gas-phase contaminants from this plume. This paper describes an experimental investigation of the effectiveness of four smokeless ashtrays: two commercial devices and two prototypes constructed by the authors. In the basic experimental protocol, one or more cigarettes was permitted to smolder in a room. Particulate or gas-phase pollutant concentrations were measured in the room air over time. Device effectiveness was determined by comparing pollutant concentrations with the device in use to those obtained with no control device. A lung deposition model was applied to further interpret device effectiveness for particle removal. The commercial ashtrays were found to be substantially ineffective in removing ETS particles because of the use of low-quality filter media and/or the failure to draw the smoke through the filter. A prototype ashtray using HEPA filter material achieved better than 90% particle removal efficiency. Gasphase pollutant removal was tested for only one prototype smokeless ashtray, which employed filters containing activated carbon and activated alumina. Removal efficiencies for the 18 gas-phase compounds measured (above the detection limit) were in the range of 70 to 95%.     

Controlled Exposures of Volunteers to Respirable Carbon and Sulf uric Acid Aerosols

Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled- environment chamber (21°C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-μm H2SO4 aerosol at =100 μg/m³, generated from water solution; (iii) 0,5-μm carbon aerosol at =250 μg/m³, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus =100 μg/m³ of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-μm size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation =50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at endexposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H₂SO₄ or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure. One individual's responses were consistent with a clinically significant excess airway constriction from H₂SO₄ plus carbon, and 2-3 others showed slight excess responses to the combined pollutants, but all these observations might have reflected chance variations. We conclude that coexisting carbon aerosol did not increase respiratory irritancy of H₂SO₄, in most healthy and asthmatic subjects exposed for 1 hr under simulated "worst-case" ambient conditions.     

Seasonal Variations in Aerosol Composition and Acidity at Shenandoah and Great Smoky Mountains National Parks

The concentration of elements Na through Pb, select ions, and organic carbon from fine (<2.5 µm) particles has been monitored at Shenandoah and Great Smoky Mountains National Parks from 1988 through 1995. The data obtained from 1988 through 1994 show that significant changes in the concentrations of many aerosol constituents occur on a seasonal basis. Particulate sulfate and organic carbon are shown to exhibit substantially higher concentrations during the summer, while sulfur dioxide and nitrate concentrations are highest during the winter.

A method for estimating the degree of neutralization of particulate sulfate is given. This method uses routinely measured aerosol elemental compositions because ammonium ion, the primary neutralizing species for sulfate, is not measured on a routine basis. Application of this method to the selected data set shows that sulfate aerosol is most acidic during summer with an average molar H_s (moles of hydrogen associated with sulfur) to S (moles of sulfur) ratio of approximately 4. This suggests the average sulfate particle during the summer has a molar coon slightly more acidic than ammonium bisulfate (NH₄HSO₄) which has a molar hydrogen to sulfur ratio of 5. Winter H_s to S ratios, however, are approximately 8, suggesting the aerosol is on average fully neutralized ammonium sulfate [(NH₄)₂SO₄].     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.