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.     

A Physical Explanation of the Lognormality of Pollutant Concentrations

Investigators In different environmental fields have reported that the concentrations of various measured substances have frequency distributions that are lognormal, or nearly so. That is, when the logarithms of the observed concentrations are plotted as a frequency distribution, the resulting distribution is approximately normal, or Gaussian, over much of the observed range. Examples include radionuclides in soil, pollutants in ambient air, Indoor air quality, trace metals In streams, metals in biological tissue, calcium In human remains. The ubiquity of the lognormal distribution in environmental processes is surprising and has not been adequately explained, since common processes in nature (for example, computation of the mean and the analysis of error) usually give rise to distributions that are normal rather than lognormal. This paper takes the first step toward explaining why lognormal distributions can arise naturally from certain physical processes that are analogous to those found in the environment. In this paper, these processes are treated mathematically, and the results are illustrated in a laboratory beaker experiment that Is simulated on the computer.     

Comparison of the Annular Denuder System and the Transition Flow Reactor for Measurements of Selected Dry Deposition Species

An intensive field study was conducted in Research Triangle Park, North Carolina in the fall of 1986. Ambient concentrations of the following constituents were obtained: nitric acid, nitrous acid, nitrogen dioxide, sulfur dioxide, ammonia, hydrogen ion, and particulate nitrate, sulfate, and ammonium. Results collected using the annular denuder system (ADS) and the transition flow reactor (TFR) are presented and compared.

Both types of samplers had operational detection limits on daily (22-hour) samples that were generally below 1 μg m_-3 suggesting that both samplers can provide sensitive measurements for most of the constituents of interest. Both the ADS and TFR show reasonable (>25 percent) within-sampler precision for most of the measured species concentrations, except TFR fine particulate nitrate measurements where results were frequently negative (The TFR fine particulate nitrate measurement is calculated using subtraction of positive numbers).

Comparison of ADS and TFR daily results showed good agreement for total particulate sulfate, the sum of total (coarse plus fine) particulate and gaseous nitrate, and ammonia. As a result of different inlet particle collection efficiencies, the ADS fine particulate sulfate exceeded the TFR (5 percent). In the absence of a filter to collect volatilized particulate ammonium in the ADS, the sum of total particulate and gaseous ammonium in the TFR exceeded that in the ADS. Of potentially more importance, ADS measurements of SO₂ and H⁺ exceeded those of the TFR, while TFR measurements of HNO₃ exceeded those of the ADS. Results of this study suggest that the TFR may provide biased measurements of SO₂, H⁺, HNO₃, and Fine NO₃ ^- that cannot be corrected without modifications to the fundamental design of the sampling system.     

Effect of Refractory on the Thermal Stability of SF6

The thermal decomposition of SF₆ is known to be oxygen-independent. Nevertheless, because of its high stability, the use of SF6 as a "conservative" surrogate in incinerator performance evaluation has been advocated and researched. This paper shows that refractory decreases markedly the stability of SF₆. The resulting increase in SF₆ decomposition was from 0 percent to 95 percent at 900°C, and the temperatures at which 90-99 percent decomposition occurred were lowered by 300-150°C. Refractory also decreased the stability of CCl₄ and C₂Cl₄, but to a lesser extent. The difference between the decompositions of C₂Cl₄ and SF₆ was reduced from several orders of magnitude to a factor of 2-4. Such a drastic and adverse change in relative stability could render SF₆ unsuitable as a "conservative" surrogate. The requirements for a "conservative" surrogate and the need for caution in its use are discussed, and further research areas are indicated.     

The Effects of Infiltration and Insulation on the Source Strengths and Indoor Air Pollution from Combustion Space Heating Appliances

Many energy conservation strategies for residences involve reducing house air exchange rates. Reducing the air exchange rate of a house can cause an increase in pollutant levels if there is an indoor pollution source and if the indoor pollutant source strength remains constant. However, if the indoor pollutant source strength can also be reduced, then it is possible to maintain or even improve indoor air quality. Increasing the insulation level of a house is a means of achieving energy conservation goals and, in addition, can reduce the need for space heating and thereby reduce the pollutant source strengths of combustion space heaters such as unvented kerosene space heaters, unvented gas space heaters, and wood stoves. In this paper, the indoor air quality trade-off between reduced infiltration and increased insulation in residences is investigated for combustion space heaters. Two similar residences were used for the experiment. One residence was used as a control and the other residence had infiltration and insulation levels modified. An unvented propane space heater was used as the source in this study. A model was developed to describe the dependence of both indoor air pollution levels and the appliance source strengths on house air exchange rates and house insulation levels. Model parameters were estimated by applying regression techniques to the data. Results show that indoor air pollution levels in houses with indoor combustion space heating pollution sources can be held constant (or lowered) by reducing the thermal conductance by an amount proportional to (or greater than) the reduction of the air exchange rate.     

Determination of Room Temperature OH Rate Constants for Acetylene,Ethylene Dichloride,Ethylene Dibromide,p-Dichlorobenzene and Carbon Disulfide

A relative rate procedure was used to measure hydroxyl rate constants at room temperature in the presence of oxygen. The photolysis of methyl nitrite in the presence of nitric oxide was used to generate OH radicals. The rate of loss of the test compounds was measured relative to that of ethane (k_OH = 2.74 × 10^-13 cm³ molec^-1 s^-1). The rates obtained at 297 ± 2 K are: acetylene = (7.8 ± 1.6) × 10^-13 cm³ molec^-1 s^-1,1,2-dichloroethane (2.8 ± Q.6) × 10^-13 cm³ molec^-1 s^-1, 1,2-dibromoethane (2.4 ± 0.5) × 10^-13 cm³ molec^-1 s^-1, p-dichlorobenzene (4.3 ± 0.9) × 10^-13 cm³ molec^-1 s^-1 and carbon disulfide (29 ± 6) × 10^-13 cm³ molec^-1 s^-1. Under a proposed EPA rule, this OH rate determination procedure could be used to determine if a given volatile organic will be subject to control for reduction of photochemical ozone.     

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 Enrichment System for Experimental Fumigation of Plants in the Field with Sulfur Dioxide

A prototype Free-Air Controlled Enrichment (FACE) system was developed at Brookhaven National "Laboratory (BNL) for the experimental control of gas concentrations in an open field, without any form of enclosure. This FACE system consists of a toroidal plenum chamber, 15 m in diameter, with a series of 32 vertical vent pipes from which the release of a test gas can be controlled. Data on gas concentration at the center of the array and wind velocity are fed to a microprocessor where a proportional, integrative, differential (PID) algorithm is used to regulate a mass-flow controller. Data on wind direction are used to control the opening and closing of the vertical vent pipes to maintain an upwind release. In 72 hours of continuous operation during which wind velocity varied between 0.3 to 8 m sec^-1, the FACE prototype maintained 1 -min averaged concentrations within twenty percent of the 40 ppb set point 94 percent of the time.     

Flow Injection Analysis of MWC Fly Ash Leaching Characteristics

Abstract

A completely mixed batch reactor leaching method utilizing flow injection analysis (the CMBR-FIA method) was developed to study the lead leaching characteristics of municipal waste combustor fly ash. Flow injection analysis (FIA) coupled with atomic absorption spectrophotometry enabled the determination of lead concentrations at one minute intervals. The pH and oxidation-reduction potential of the solution were continuously monitored to characterize the leaching conditions. Automatic titration was used to alter the solution pH to defined endpoints. The CMBR-FIA method offers the ability to immediately observe alterations to the leaching solution, and grants the freedom to study a number of parameters concurrently. The CMBR-FIA method is a rapid and reliable means to investigate leaching characteristics. This paper describes the method and demonstrates its use to monitor the leaching of lead from municipal solid waste combustor fly ash as a function of pH. Soluble lead concentrations are shown to increase quickly with decreasing pH.

A maximum of 50% of the total lead concentration was available in solution at pH 2. This value gradually decreased with time to over 35% of the total.