Mathematical Model for Photocatalytic Destruction of Organic Contaminants in Air

Abstract

Photocatalytic oxidation (PCO) was investigated in a bench-scale reactor for the abatement of two airborne organic contaminants: toluene and ethanol. A mathematical model that includes the impacts of light intensity, initial contaminant concentration, catalyst thickness, and relative humidity (RH) on the degradation of organic contaminants in a photocatalytic reactor was developed to describe this process. The commercially available catalyst Degussa-PtTiO₂ was selected to compare with the MTU-PtTiO₂-350 catalyst, which was synthesized by the sol-gel process, platinized, and calcined at 350 °C. For toluene removal using the MTU-PtTiO₂-350 catalyst, the degradation rate increased with increases in light intensity from 0.2 to 2.2 mW/cm² and in catalyst thickness from 0.00037 to 0.00361 cm. However, further increases in light intensity and catalyst thickness had only slight effect on the toluene degradation rate. Increasing the initial concentration from 6.29 to 127.9 μg/L and the RH from 10 to 85% resulted in decreases in the toluene degradation rate. For ethanol removal using the MTU-PtTiO₂- 350 catalyst, the degradation rate increased more rapidly with an increase in RH from 17 to 56%; the RH had little effect on the ethanol degradation rate while it further increased from 56% to 82%. We discuss applicability of the model to estimate the influence of process variables and to evaluate photocatalyst performance.     

Standards for Air Quality in California

Abstract

During the 1950s and 1960s, hundreds of thousands of underground storage tanks (and above-ground storage tanks) containing petroleum products and hazardous chemicals were installed. Many of these tanks either have been abandoned or have exceeded their useful lives and are leaking, thereby posing a serious threat to the nation’s surface and groundwater supplies, as well as to public health. Cleaning up releases of petroleum hydrocarbons or other organic chemicals in the subsurface environment is a real-world problem,

Biological treatment of hydrocarbon-contaminated soil is considered to be a relatively low-cost and safe technology; however, its potential for effectively treating recalcitrant wastes has not been fully explored. For millions of years, microorganisms such as bacteria, fungi, actinomycete, protozoa, and others have performed the function of recycling organic matter from which new plant life can grow.

This paper examines the biological treatment technology for cleaning up petroleum product-contaminated soils, with special emphasis on microbial enzyme systems for enhancing the rate of biodegradation of petroleum hydrocarbons. Classifications and functions of enzymes, as well as the microbes, in degrading the organic contaminants are discussed. In addition, the weathering effect on biodegradation, types of hydrocarbon degraders, advantages associated with enzyme use, methods of enzyme extraction, and future research needs for development and evaluation of enzyme-assisted bioremediation are examined.     

APM-3 Recommended Standard Methods for Continuing Air Monitoring for Gaseous Contaminants

The purpose of Manual APM-3 is to provide a guide which will help increase the uniformity between various surveys, and thereby increase the useability of the data by others.     

Advances in the Analysis of Air Contaminants Comments

Abstract

Methylcyclopentadienyl manganese tricarbonyl (MMT) is an organometallic compound used as an octane improver in unleaded gasoline. The combustion of MMT leads to the formation of manganese (Mn) oxides, mainly Mn₃O₄. The objective of this study is to assess the variations over time and space of respirable (Mn_R) and total (Mn_T) Mn in the urban atmosphere and to evaluate human exposure by inhalation. Two sampling sites were selected on the island of Montreal based on their local traffic density (municipal botanical garden, C^-= 10,000–15,000 vehicles d^-1; Montreal Waterworks, C⁺= 100,000–130,000 vehicles d^-1). Air samplings were made during the day at stations located 10 m from the road using portable pumps, some of which were equipped with a cyclone. Mn_R and Mn_T and other metals were measured on Teflon filters by neutron activation. Mn exposure doses by inhalation were calculated using Monte–Carlo simulations. Mn_R and Mn_T average concentrations were significantly higher at site C⁺ (Mn_R = 0.024 µg m^-3; Mn_T = 0.050 µg m^-3) than at site C^- (Mn_R= 0.015 µg m^-3; Mn_T= 0.027 µg m^-3). Temporal profiles at sites C⁺ and site C^-were similar, with a coefficient of correlation of 0.24 for Mn_R and 0.26 for Mn_T. Trend analyses (ARIMA) also showed that the period of the week (work days vs. off days) was significantly related to Mn_R and Mn_T variations at both sites. The average exposure dose by inhalation to Mn_R and Mn_T ranged from 0.001 to 0.030 µg kg^-1 day^-1 and 0.001 to 0.05 µg kg^-1 day^-1. Mn_R and Mn_T concentrations reflected a positive relationship with traffic density. However, it remains difficult to attribute these results directly to the combustion of MMT in unleaded gasoline. On average, the Mn_R and Mn_T inhalation doses were 2 to 15 times lower than the reference dose (RfC) proposed by the U.S. Environmental Protection Agency (EPA) for the general population.     

Air Quality Standards for Fluoride Vegetation Effects

Facts that must be taken into consideration in developing fluoride standards for vegetation effects include: (1) Fluoride is an accumulative toxicant and injury is usually associated with long-term exposure; (2) gaseous and particulate fluorides differ in their phytotoxicity; (3) plant species and varieties differ greatly in susceptibility to fluoride; (4) extremely low concentrations can cause damage to sensitive species. Three possible approaches to standards are discussed: Atmospheric fluoride concentration, vegetation fluoride concentration, and the presence of leaf necrosis or chlorosis. Atmospheric fluoride concentration has the advantage that it fits the conventional concept of standards and that it is objective. Accurately measuring low fluoride concentrations, separating gaseous from particulate fluorides in the air sample, and establishing a safe concentration present technical problems, however. Vegetation analysis may more closely represent fluorides available to affect the plant. The presence of significant amounts of fluoride-induced leaf necrosis (e.g., 3% of the leaf area) may be the most practical approach to standards for fluoride vegetation effects. Advantages are that the combined effects of the forms of fluoride, species and varieties, and concentration-time relationships are all manifest in the factor that is measured. Relatively little time is required to examine the vegetation in a large area and only 2 or 3 surveys a year are required.     

Canister-Based Method for Monitoring Toxic VOCs in Ambient Air

The availability of reliable, accurate and precise monitoring methods for toxic volatile organic compounds (VOCs) is a primary need for state and local agencies addressing daily monitoring requirements related to odor complaints, fugitive emissions, and trend monitoring. The canister-based monitoring method for VOCs is a viable and widely used approach that is based on research and evaluation performed over the past several years. This activity has involved the testing of sample stability of VOCs in canisters and the design of time-integrative samplers. The development of procedures for analysis of samples in canisters, including the procedure for VOC preconcentration from whole air, the treatment of water vapor in the sample, and the selection of an appropriate analytical finish has been accomplished. The canister-based method was initially summarized in the EPA Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air as Method TO-14. Modifications and refinements are being added to Method TO-14 in order to obtain a Statement of Work for the Superfund Contract Laboratory Program for Air. This paper discusses the developments leading to the current status of the canisterbased method and provides a critique of the method using results obtained in EPA monitoring networks.     

Atmospheric Chemistry of Toxic Contaminants 1. Reaction Rates and Atmospheric Persistence

Using structure-reactivity relationships between reaction rate constants and ionlzatlon potentials for structural homologues, estimates are presented for the rate constants of the reactions of ozone, the hydroxyl radical, and the nitrate radical with forty toxic air contaminants for which no or little data are available. These rate constants are in turn used to estimate the atmospheric persistence of saturated allphatics, unsaturated allphatics, and aromatic toxic organics. The corresponding atmospheric half-lives for removal by chemical reactions range from a few hours for the most reactive toxics (chloroprene, hexachlorocyclo-pentadiene, cresols, nitrosamines, maleic anhydride) to several months for the least reactive compounds (nitrobenzene, methyl bromide, phosgene).     

Are We Ready for Ambient Air Quality Standards

The legal basis for the control of air pollution has progressed from nuisance law to the statutory regulation of specific substances as the sophistication of the sciences involved has progressed. But, the control of air pollution by pursuing air pollutants one by one as evidence accumulates against them seems clearly inadequate to a technology producing new pollutants at an almost geometric rate and inappropriate to the gathering body of evidence relating air pollution to health effects. To understand the need for changed control concepts it is necessary to understand the biological problem and the evidence that has been accumulated.     

Selected International Receptor-Based Air Quality Standards

Abstract

The ambient air quality standards (AAQS) of twenty-one nations for eight commonly regulated substances are presented. Many countries are adding a receptor-based component to their air quality management, which traditionally have been emission oriented. Automation of air quality monitoring stations has meant that local air quality evaluation can now be more easily achieved. However, a majority of countries have no active air quality standards (emission or receptor-based) or ambient air quality monitoring. One possible monitoring procedure is outlined and the variation in international standards is discussed.     

Air Quality Standards National And International

The advantages and disadvantages of establishingworldwide air quality standards are reviewed. Inter-national standards would represent the best and mostadvanced procedures and might lead to improvementin standards in some countries where air quality isfar from adequate. International standards alsowould permit accurate comparisons of air pollutionamong countries and would provide a sound basis forcombatting pollution.     

California Experience with Air Quality Standards

Air quality standards have existed in California for almost six years. They have become an important part of the State’s air pollution control program.

The two principal uses of the standards have been to establish the goals for controlling motor vehicle emissions and to provide a basis for evaluating air quality throughout the State. The standards have also proved to be valuable as a means of communicating on air pollution problems with legislators, administrators, the press, the public, and dischargers of pollutants.

Lack of adequate data on the effects of varying concentrations of contaminants of concern in air pollution is a serious limitation in any effort to establish air quality standards.It is important that this data be obtained.

The concept of employing air quality standards as administrative goals is not unique to the air pollution field but is part of a broad trend to utilize standards for insuring a satisfactory environment. Those engaged in the air pollution field can expect to see increasing emphasis on such standards.

Air quality standards do not provide a magic formula for eliminating air pollution; they are but one element in a comprehensive program. They have limitations and are no better than the data upon which they are based. The standards, however, can play an important role in preserving satisfactory air quality and protecting man’s health.

In using air quality standards, one should keep in mind the comments of H. W. Streeter⁵ on water quality standards—“Let us devise them, try them, revise them, and apply them, but also remember that they are but ’feeble instruments of the human will’ and like all other such tools are made to be discarded for better ones when they become worn out.“     

Atmospheric Chemistry of Toxic Contaminants. 6. Nitrosamines: Dialkyl Nitrosamines and Nitrosomorpholine

Detailed mechanisms are outlined for the reactions that contribute to in-sltu formation and atmospheric removal of dlmethylnitrosamine, diethylnitrosamlne, methyl-ethylnltrosamine, and nitrosomorphollne. In-sltu formation involves the rapid reaction of amines with the hydroxyl radical, leading to nltrosamlnes, nltramlnes, amides, and aldehydes. Nitrosamlne photolysis accounts for their rapid daytime removal, leading to amlno radicals whose atmospheric reactions are also discussed.     

Codependencies of Reactive Air Toxic and Criteria Pollutants on Emission Reductions

Abstract

It is important to understand the effects of emission controls on concentrations of ozone, fine particulate matter (PM_2.5), and hazardous air pollutants (HAPs) simultaneously, to evaluate the full range of health, ecosystem, and economic effects. Until recently, the capability to simultaneously evaluate interrelated atmospheric pollutants (“one atmosphere” analysis) was unavailable to air quality managers. In this work, we use an air quality model to examine the potential effect of three emission reductions on concentrations of ozone, PM_2.5, and four important HAPs (formaldehyde, acetaldehyde, acrolein, and benzene) over a domain centered on Philadelphia for 12-day episodes in July and January 2001. Although NO_x controls are predicted to benefit PM_2.5 concentrations and sometimes benefit ozone, they have only a small effect on formaldehyde, slightly increase acetaldehyde and acrolein, and have no effect on benzene in the July episode. Concentrations of all pollutants except benzene increase slightly with NO_x controls in the January simulation. Volatile organic compound controls alone are found to have a small effect on ozone and PM_2.5, a less than linear effect on decreasing aldehydes, and an approximately linear effect on acrolein and benzene in summer, but a slightly larger than linear effect on aldehydes and acrolein in winter. These simulations indicate the difficulty in assessing how toxic air pollutants might respond to emission reductions aimed at decreasing criteria pollutants such as ozone and PM_2.5.     

Screening Models for Estimating Toxic Air Pollution Near a Hazardous Waste Landfill

This paper is directed to environmental scientists concerned with assessing toxic air pollution downwind of hazardous waste landfills to determine whether potential health threats or exceedances of air quality standards exist. The purpose of this paper is to evaluate the performance of four air quality screening models.

The emission rate of vinyl chloride from the BKK co-disposal landfill in West Covina, California is estimated. Ambient vinyl chloride concentrations are estimated using a ground level point source model, two virtual point source models, arid the simple box model with meteorological and landfill input data representative of periods when ambient monitoring was conducted. The two virtual point source models are most precise and accurate in estimating 24-hour vinyl chloride concentrations. However, the results could include compensating errors in the emission rate and dispersion calculations because the emission rate estimate could not be independently evaluated.     

An Approach to Air Quality Management Standards

The Clean Air Amendments of 1970 impose a stringent set of uniform air quality standards and a rigid timetable for achieving them. Such an approach is open to serious question, since it fails to take account of variations in relevant local conditions. This paper sketches a proposal for a more realistic approach to air quality. It suggests a program of management standards that would reflect the needs and circumstances of particular regions. An institutional framework is outlined that would consider the technical, economic, and social constraints that determine how quickly and how much any area can improve its air quality. The framework would provide the needed flexibility, and would employ a feedback approach that avoids the need to resolve all uncertainties before any progress can be made. At the same time, it would impose a timetable and planning process to assure that all feasible progress in air quality improvement is realized nationwide.