The electron density distribution in pyridinium and bipyridylium compounds and its relevance to their adsorption by expanding lattice clays

Abstract

Charge distributions in 1, 1'‐ethylene‐2, 2'‐bipyridylium (diquat), 1,1'‐dimethyl‐4,4'‐bipyridylium (paraquat) and 1‐methylpyridinium organocations were calculated by a Complete Neglect of Differential Overlap semi‐empirical quantum mechanical procedure. The data show that the positive charges in the organocations are distributed around the molecules and are greatest in the positions ortho and para to the heterocyclic nitrogen atoms. Earlier interpretations of the mechanisms of adsorption of paraquat and diquat by soils and clays assumed that the charges were located in the heterocyclic nitrogen atoms. Here some consideration is given to the influence of the charge delocalizations on the processes of adsorption by montmorillonite and vermiculite clay preparations.     

HCI Sorption by Dry NaHCO3 for Incinerator Emissions Control

The sorption of hydrochloric acid (HCI) by thermally decomposed sodium bicarbonate (NaHCO₃) was investigated using a fixed-bed reactor containing sorbent particles dispersed in a bed of spherical glass beads. The gas flow rate (68° F and 760 mm Hg) was 0.039 cfm (1.1 liter/min) and the bed had a cross-sectional area of 0.0055 sq. ft. (5.1 sq. cm). The influence of particle diameter (10, 45 and 163 μm), temperature (225, 275, 375, 455, and 550° F), superficial gas velocity (11 and 21 fpm at reactor conditions, 375° F), and Inlet HCI gas concentration (415 ppm and 760 ppm in N₂, 275 and 455° F) were studied. Results showed that HCI sorption increased strongly with increasing temperature but was only weakly dependent on particle diameter, superficial gas velocity, and HCI gas concentration.     

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.     

Moving Bed Adsorption System for Control of VOCs from an Aircraft Painting Facility

An activated carbon moving bed system (10 to 100 acf m air flow) was tested for controlling VOC emissions from a commercial aircraft painting facility. The cross-flow moving adsorbent bed showed a VOC collection efficiency in the 77.1 to 99.6 percent range over a superficial gas velocity range of 27 to 185 ft/min (0.14-0.94 m/sec). The collection efficiencies were neither affected by a change in carbon flow rates from 5 to 8 Ib/hr (2.3 to 3.6 kg/hr) nor by a change in the gas superficial velocity from 27 to 185 ft/min. The VOC concentration in the emission stream from the painting hangar was found to vary by at least a factor of 20 (from 0.18 to 15 ppm) both over the five month period (during which the 15 system tests of about three hours each were conducted) and within a single eight hour work shift.     

A Comparative Analysis of Emissions Deterioration for In-Use Alternative Fuel Vehicles

Abstract

Although there have been several studies examining emissions from in–use alternative fuel vehicles (AFVs), little is known about the deterioration of these emissions over vehicle lifetimes and how this deterioration compares with deterioration from conventional vehicles (CVs). This paper analyzes emissions data from 70 AFVs and 70 CVs operating in the federal government fleet to determine whether AFV emissions deterioration differs significantly from CV emissions deterioration. An analysis is conducted on three alternative fuel types (natural gas, methanol, and ethanol) and on four pollutants (carbon monoxide, total hydrocarbons, non-methane hydrocarbons, and nitrogen oxides). The results indicate that for most cases studied, deterioration differences are not statistically significant; however, several exceptions (most notably with natural gas vehicles) suggest that air quality planners and regulators must further analyze AFV emissions deterioration to properly include these technologies in broader air quality management schemes.     

Estimation of Trends in Atmospheric Concentrations of Sulfate in the Northeastern United States

Abstract

Daily atmospheric concentrations of sulfate collected at six locations in the northeastern United States are regressed against meteorological factors, ozone, seasonal cycles, and time in order to determine if a significant trend in sulfate can be detected. The data used in this analysis were collected during the Sulfate Regional Experiment (SURE, 1977-1978) and the Eulerian Model Evaluation Field Study (EMEFS, 1988-1989). Ozone, specific humidity, and seasonal terms (reflecting the potential of the atmosphere for oxidation of sulfur dioxide) emerged as important explanatory variables. After accounting for the variability explained by environmental factors, the median estimated change in sulfate concentration from the six locations over the 11-year period is -22% (or -28% if ozone is not used as an explanatory variable). Although there are wide variations among locations, these changes are commensurate with an estimated 25% decline in sulfur emissions in the northeastern U.S. during the same period. These analyses provide insight into methods for detecting reductions in sulfate that may be expected to occur as a result of the Clean Air Act Amendments of 1990. Uncertainties in the estimates, with consideration of serial correlation in the data, imply a minimum detectable reduction of 10% using this modeling procedure with similar data availability.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Validation of the Digital Opacity Compliance System under Regulatory Enforcement Conditions

Abstract

U.S. Environmental Protection Agency (EPA) Emission Measurement Center in conjunction with EPA Regions VI and VIII, the state of Utah, and the U.S. Department of Defense have conducted a series of long-term pilot and field tests to determine the accuracy and reliability of a visible opacity monitoring system consisting of a conventional digital camera and a separate computer software application for plume opacity determination. This technology, known as the Digital Opacity Compliance System (DOCS), has been successfully demonstrated at EPA-sponsored Method-9 “smoke schools,” as well as at a number of government and commercially operated industrial facilities.

Results from the current DOCS regulatory pilot study demonstrated that, under regulatory enforcement conditions, the average difference in opacity measurement between the DOCS technology and EPA Reference Method 9 (Method 9) was 1.12%. This opacity difference, which was computed from the evaluation of 241 regulated air sources, was found to be statistically significant at the 99% confidence level. In evaluating only those sources for which a nonzero visible opacity level was recorded, the average difference in opacity measurement between the DOCS technology and Method 9 was 1.20%. These results suggest that the two opacity measurement methods are essentially equivalent when measuring the opacity of visible emissions.

Given the costs and technical limitations associated with use of Method 9, there is a recognized need to develop accurate, reproducible, and scientifically defensible alternatives to the use of human observers. The use of digital imaging/processing brings current technology to bear on this important regulatory issue. Digital technology offers increased accuracy, a permanent record of measurement events, lower costs, and a scientifically defensible approach for opacity determination.