Influence of uncertain reaction rates on ozone sensitivity to emissions

Air quality models rely upon simplified photochemical mechanisms to efficiently represent the thousands of chemical species that interact to form air pollution. Uncertainties in the chemical reaction rate constants and photolysis frequencies that comprise those mechanisms can generate uncertainty in the estimation of pollutant concentrations and their responsiveness to emission controls. A high-order sensitivity analysis technique is applied to quantify the extent to which reaction rate uncertainties influence estimates of ozone concentrations and their sensitivities to precursor emissions during an air pollution episode in Houston, Texas. Several reactions were found to have much larger proportional effects on ozone’s sensitivities to emissions than on its concentrations. In particular, uncertainties in photolysis frequencies and in the rate of reaction between NO₂ and OH to form nitric acid can significantly influence the magnitude and sign of peak ozone sensitivity to nitrogen oxide (NO_x) emissions. Ozone sensitivity to VOCs exhibits a much more muted response to uncertainties in the reaction rate constants and photolysis frequencies considered here. The results indicate the importance of accurate reaction rate constants to predicting the ozone impacts resulting from NO_x emission controls.     

Diflubenzuron residue and persistence on an oak forest after aerial application

Abstract

A twenty hectare forest block in central Pennsylvania was aerially sprayed with diflubenzuron (Dimilin 25W®) at the dose of 33.23g A.I./ha in 9.4 litres/ha. Leaf samples were collected from the upper and lower canopies of 27 oaks and understory within this block on the day of spray, May 29, 1991. Canopy leaves were also collected on May 31, June 10, July 29 and September 26, 1991.

Recovery of diflubenzuron residues on fortified canopy‐leaf and litter‐leaf samples using analytical techniques employed in this study averaged 87.4% (SE = 7.5%) and 66.2% (SE = 8.2%), respectively.

On the day of spray, diflubenzuron residues on the upper canopy, lower canopy and understory averaged 81.18, 39.65 and 8.35 ng/cm², respectively. Diflubenzuron residues on canopy‐leaf samples collected 2, 12, 61 and 120 days post‐spray averaged 14.83 (SE = 10.19), 16.75 (SE = 9.95), 12.84 (SE = 8.25) and 11.20 (SE = 7.52) ng/cm², respectively. Diflubenzuron residues on litter‐leaf samples collected after leaf senescence ‐ 169 and 323 days post spray contained measurable amounts of diflubenzuron in 51 and 59% of the samples, respectively. Of the samples with measurable amounts of diflubenzuron, residues averaged 1.36 (SE = 2.44) and 0.65 ng/cm² (SE = 0.73) respectively.     

Biological nitrogen and carbon removal in a gravity flow biomass concentrator reactor for municipal sewage treatment

A novel membrane system, the Biomass Concentrator Reactor (BCR), was evaluated as an alternative technology for the treatment of municipal wastewater. Because the BCR is equipped with a membrane whose average poresize is 20 μm (18–28 μm), the reactor requires low-pressure differential to operate (gravity). The effectiveness of this system was evaluated for the removal of carbon and nitrogen using two identical BCRs, identified as conventional and hybrid, that were operated in parallel. The conventional reactor was operated under full aerobic conditions (i.e., organic carbon and ammonia oxidation), while the hybrid reactor incorporated an anoxic zone for nitrate reduction as well as an aerobic zone for organic carbon and ammonia oxidation. Both reactors were fed synthetic wastewater at a flow rate of 71 L d^?1, which resulted in a hydraulic retention time of 9 h. In the case of the hybrid reactor, the recycle flow from the aerobic zone to the anoxic zone was twice the feed flow rate. Reactor performance was evaluated under two solids retention times (6 and 15 d). Under these conditions, the BCRs achieved nearly 100% mixed liquor solids separation with a hydraulic head differential of less than 2.5 cm. The COD removal efficiency was over 90%. Essentially complete nitrification was achieved in both systems, and nitrogen removal in the hybrid reactor was close to the expected value (67%).     

A preliminary examination of the translocation of microencapsulated cyfluthrin following applications to the perimeter of residential dwellings

Abstract

Methods have been developed to monitor the translocation of microencapsulated cyfluthrin following perimeter applications to residential dwellings. A pilot study was implemented to determine both the potential for application spray to drift away from dwellings and the intrusion of residues into homes following perimeter treatments. Residential monitoring included measuring spray drift using cellulose filter paper and the collection of soil samples from within the spray zone. In addition, interior air was monitored using fiberglass filter paper as a sorbent medium and cotton ball swabs were used to collect surface wipes.

Fortification of matrixes resulted in recoveries of >90%. Spray drift was highest at the point of application and declined to low but measurable levels 9.1m from the foundations of dwellings. Soil residues declined to low, but measurable levels by 45 days post‐application. No cyfluthrin was measured from indoor air; however, some interior surfaces had detectable levels of cyfluthrin until three days post‐application.

Findings indicate that spray drift resulting from perimeter applications might contaminate non‐target surfaces outside the spray zone. Soil borne residues may serve as persistent sources for human exposure and potentially intrude into dwellings through the activities of occupants and pets. Residues do not appreciably translocate through air and consequently inhalation is not a likely route for human exposure. Surface residues detected indoors suggest that the physical movement of residues from the exterior to the interior might be a viable route of movement of residues following this type of application.     

A Note on Comparison of Statistical and Analytical Results for Calculating Oxides of Nitrogen Concentrations

A question often asked about analytical diffusion models is “How do the analytical results for calculating pollution concentrations compare with those obtained by statistical techniques?” Miller and Holzworth (1967) have developed a simple analytical diffusion model that yields relative pollution concentrations, x/Q, as a function of afternoon mixing depth, mean transport wind speed, and city size. This analytical model may also be used in reverse to determine apparent afternoon source strengths from observed afternoon pollution concentrations. The apparent source strengths may then be used with the model on independent data to estimate pollution concentrations. It is the purpose of this note to compare results of calculating average afternoon concentrations of oxides of nitrogen (NO_x) by use of the Miller-Holzworth model with those obtained from statistical regression equations.     

An Atmospheric Diffusion Model for Metropolitan Areas

An urban diffusion model, which does not require the use of an electronic computer, is presented. The main simplifying assumptions are that continuous pollutant sources are uniformly distributed over the urban area and vertical diffusion occurs until the effluent from each line source reaches the top of the mixing layer, after which the effluent is uniformly distributed through the mixing layer. After the appropriate vertical diffusion coefficient is specified, the calculated concentration is a function of source strength, linear dimension of the metropolis, mixing depth, and wind speed. The calculated concentration is interpreted either as a representative maximum concentration or, through integration, as the average concentration over the metropolitan area. When a representative pollutant concentration is known, the model may be used to determine the apparent “uniform” source strength.     

Ozone Dosage Response of Ponderosa Pine Seedlings

Photochemical oxidant injury to ponderosa pine (Pinus ponderosa Laws) is a severe problem in the southern California mountains. Three-year-old ponderosa pines fumigated in controlled environment chambers with ozone at 0.15, 0.30, or 0.45 ppm had apparent photosynthesis rates reduced by 10, 70, and 85%, respectively, after 30 days exposure. A fumigation with 0.30 ppm ozone for 33 days depressed the cold perchloric acid extracted polysaccharides of both current and one-year-old needles by 40%. The 80% ethanol soluble sugar concentration of current year, ozone-injured needles increased 16% and that of the one-year-old needles decreased slightly. Both carbohydrate fractions of control trees in carbon-filtered air increased moderately. Higher, endogenous concentrations of ascorbic acid in needles did not protect the tissue from ozone injury. Apparent photosynthesis rate was a sensitive index for ozone dosage response. Needle carbohydrate depletion probably induces premature abscission.     

The Removal of Particulate Matter from Fluid Bed Catalytic Cracking Unit Stack Gases

The application of a high-efficiency centrifugal type of separator to fluid bed catalytic cracking units is described in which most of the catalyst particles often lost to the atmosphere are concentrated into a small part of the stack gas (2%). A further separation can then be made on this small stream by an auxiliary separator which further concentrates the catalyst particle into 0.1% of the initia stream. Performance of the main and auxiliary separators are such as to reduce the loss of catalyst particles in the stack gas from 800 ppm to less than 60 ppm in a typical unit. Large amounts of power can be recovered by application of expander turbines to catalytic cracking plants employing this system of separation.     

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.     

Transmissometer Measurement of Participate Emissions from a Jet Engine Test Facility

The body of information presented in this paper is directed toward those individuals involved with handling hazardous materials, whether in actual use of such chemicals, or in monitoring atmospheric emissions. Although specifically relating experience in the design and testing of phosgene emission control equipment, it attempts to establish general guidelines for effectively dealing with emissions of hazardous materials. An approach for handling chemical pollutants having no established air quality emission standards is developed. The paper presents a technique for establishing process emissions at acceptably low levels to insure the health and safety of the general population as well as that of the process workers themselves. Methods, suitable for measuring phosgene at these low levels, have been investigated, and problems associated with such an investigation are discussed. While complete theoretical scrubber design criteria are beyond the scope of this paper, many of the "real world" problems which affected scrubber performance are presented. Finally, the practical aspects of process emissions control are illustrated by actual results from the system test.