Reducing Interference Effects in the Chemiluminescent Measurement of Nitric Oxides from Combustion Systems

Experiments were carried out to determine the relative chemiluminescence quenching efficiencies as a function of third body concentration for each of the common combustion products, H₂O, CO₂, CO, H₂, O₂ and Ar. These results are compared with those of other investigators. The effect of reaction chamber pressure on analyzer response and the development of an analyzer design which incorporates an adjustable sample capillary inlet capable of maintaining a constant molar flow rate of sample gas to the reaction chamber are discussed. The effect of carbon monoxide interference on chemiluminescent NO_x measurement has been isolated and found to be significant. A means of correcting NO, measurements for these CO interference effects is described. Quantification of NO and NO₂ absorption in liquid water in NO_x sampling systems has been made. Recommendations for sample system designs to handle the presence of water in the sample gas are made.     

An Evaluation of the Effects of Ozone Injury on Radial Growth of Ponderosa Pine (Pinus ponderosa) in the Southern Sierra Nevada

Growth of ponderosa pines with visible symptoms of ozone injury was compared with that of asymptomatic trees in the southern Sierra Nevada, California. Time series analysis indicated that there was no significant reduction in annual radial increment of symptomatic trees during recent years compared to past growth and growth of asymptomatic trees. First order autocorrelation and climatic variables accounted for a large proportion of the variance in growth index, and winter precipitation was positively correlated with growth for all size and age classes. Although ozone concentrations are high enough to cause chlorosis and premature needle senescence in ponderosa pine, there has been no significant change in growth associated with ozone injury.     

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.     

Speciation of Arsenic in Ambient Aerosols Collected in Los Angeles

First-time measurements of the potentially toxic inorganic species of arsenic (arsenite arid arsenate) have been obtained in fine (<2.5 µm AD) and coarse (>2.5 µm AD) atmospheric particles in the Los Angeles area. A recently developed method that includes procedures for sample collection, preparation, and analysis was used in this study. Size-fractlonated aerosol samples were collected with a high-volume dichotomous virtual impactor that employed polytetrafluoroethylene filters. Results were obtained for the recovery of arsenic standards added to unexposed and collected filters. Data from this study, indicated that the recently developed speciation method can be used to determine concentrations of As(lll) and As(V) In atmospheric particulate matter samples.

Size-fractionated aerosol samples were collected in the city of Industry during January and February 1987. In most samples, As(lll) and As( V) were above the detection limit (approximately 1 ng m^-3 of either species) in both aerosol size fractions. A greater portion (about 75 percent) of the two species were observed in the fine particles. The As(lll)/As(V) ratio for both particle sizes was close to 1 (I.e., an equal mixture of both species). Comparison of total suspended particulate arsenic measured by the speciation method to that measured by a routine California Air Resources Board-approved procedure showed good agreement (r = 0.94), indicating both methods were approximately equivalent for the collection and analysis of aerosol arsenic.     

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.     

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.     

Rotary Kiln Incineration III. An Indepth Study—Kiln Exit/Afterburner/Stack Train and Kiln Exit Pattern Factor Measurements During Liquid CCl4 Processing

Temperature and stable species concentration data are presented from various locations within a full-scale rotary kiln incinerator firing natural gas/carbon tetrachloride/air. The data are being collected as part of a cooperative program involving university, industry and government participation. The overall goal of the program is to develop a more sophisticated understanding of and a predictive capability for rotary kiln and afterburner performance as influenced by basic design and operational parameters. Non-uniformities in stable species and temperature exist for this particular kiln, at the kiln exit, under certain operating conditions. Flow perturbations from within the kiln were found to persist into the afterburner, but not into the stack. High destruction and removal efficiencies (DRE’s) were achieved under the operating conditions of these tests through adequate secondary combustion processing.     

Rotary Kiln Incineration IV. An Indepth Study— Kiln Exit,Transition and Afterburner Sampling During Liquid CCl4 Processing

Detailed temperature and stable species concentration data are presented from the kiln exit, transition section and afterburner of a full-scale incinerator facility firing natural gas/carbon tetrachloride/air. The data are collected as part of a cooperative program involving university, industry and government participation. The overall goal of the program is to develop an understanding and predictive capability for rotary kiln and afterburner performance as influenced by basic design and operational parameters. The data demonstrate that nonuniformities in stable species and temperature exist, under certain operating conditions, at the kiln exit in the vertical direction only. Measurements from the transition section indicate that non-uniformities may exist within this region under certain operating conditions. Flow perturbations from within the kiln can persist into the afterburner, although the degree of nonuniformity is substantially reduced compared to either the kiln or transition sections. High destruction and removal efficiencies were achieved under all operating conditions of these tests through a combination of kiln and secondary combustion processing.