An Evaluation of the Kriging Method to Predict 7-h Seasonal Mean Ozone Concentrations for Estimating Crop Losses

Using kriging, a statistical technique, the National Crop Loss Assessment Network (NCLAN) program estimated growing season 5-month (May-September) ambient 7-h mean O₃ concentrations for each of the major crop growing areas of the United States for 1978-1982. The O₃ estimates were used to predict economic benefits anticipated by lowering O₃ levels in the United States. This paper reviews NCLAN’s use of kriging to estimate 7-h seasonal mean O₃ concentrations for crop growing regions. Although the original kriging program used by NCLAN incorrectly calculated the diagonal elements of the kriging equations, this omission did not result in significant errors in the predicted estimates. Most of the data used in estimating the 7-h seasonal values were obtained from urban areas; the use of these data tended to underestimate the 7-h seasonal O₃ concentrations in rural areas. It is recommended that only O₃ data that are representative of agricultural areas and have been collected under accepted quality assurance programs be used In future kriging efforts.     

Tank Atmosphere Perturbation: A Procedure for Assessing Flashing Losses from Oil Storage Tanks

Abstract

A new procedure to measure the total volume of emissions from heavy crude oil storage tanks is described. Tank flashing losses, which are difficult to measure, can be determined by correcting this value for working and breathing losses. The procedure uses a fan or blower to vent the headspace of the storage tank, with subsequent monitoring of the change in concentrations of oxygen or other gases. Combined with a separate determination of the reactive organic carbon (ROC) fraction in the gas, this method allows the evaluation of the total amount of ROC emitted. The operation of the system is described, and results from measurement of several storage tanks in California oil fields are presented. Our measurements are compared with those obtained using the California Air Resources Board (CARB) 150 method.     

The Characterization of Ozone and Sulfur Dioxide Air Quality Data for Assessing Possible Vegetation Effects

Since the 1960s, much effort has been devoted to collecting and formatting air quality data. This paper discusses 1) the availability of air quality data for assessing potential biological impacts associated with ozone and sulfur dioxide ambient exposures, 2) examples of how air quality data can be characterized for assessing vegetation effects, and 3) the limitations associated with some exposure parameters used for developing relevant vegetation doseresponse yield reduction models. Data are presented showing that some ozone monitoring sites not continuously affected by local urban sources experience consecutive hourly ozone exposures ≥0.10 ppm in the late evening and early morning hours. These sites experience their maximum ozone concentrations either in the spring or summer months. Sites influenced by local rural sources experience their maximum ozone concentrations during the summer months. It is suggested that further research be performed to identify whether the sensitivity of a target organism at the time of exposure, as well as the pollutant concentration and chemical form that enters into the target organism, is as important in defining effects as air pollutant exposure alone.     

A Regujatory Framework for Setting Air Emission Limits for Noncriteria Pollutants

The information presented in this paper is concerned with the effects of ambient ozone on crop yield reduction and the resultant economic losses. Yield data for nine crops within the South Coast Air Basin (SCAB) of California were obtained for the 12-year period, 1964 through 1975. Ozone concentrations, temperature, precipitation, and relative humidity data were related to the yields by using regression models. Estimated yield reductions due to ozone for 1975, varied from zero to 57% depending on crop and location. Economic welfare losses calculated from the yield reductions were $57.3 and $45.7 million for producer’s and consumer’s surplus, respectively. The total loss from ozone to agriculture related economic sectors determined by input-output analysis was $276 million in the SCAB and $36.6 million in the remainder of the state.     

Predicting Respiratory Morbidity from Pulmonary Function Tests: A Reanalysis of Ozone Chamber Studies

Some consequences of acute exposure to ozone are best measured In studies of human respiratory responses in controlled exposure chambers. These studies typically examine relationships between exposures to alternative pollutant concentrations and Indicators of lung function as measured by spirometry, such as forced expiratory volume In one second, FEV₁ However, the association of respiratory morbidity with these changes In lung function is not well established. To gain a better understanding of the relationship between ozonerelated changes in pulmonary function and respiratory symptoms, data from several clinical studies have been reanalyzed. Logistic regression models were used to determine the quantitative relationship between changes in FEV₁ and the probability of a mild or moderate lower respiratory symptom. Models were developed that corrected for repeated sampling of individuals and both population-averaged and subject-specific effects were determined. The results indicate the existence of a strong and consistent quantitative relationship between changes in lung function and the probability of a respiratory symptom. Specifically, a 10 percent reduction in FEV₁ is associated with a 15 percentage point increase In the probability of a mild, moderate or severe lower respiratory symptom and a 6 percentage point increase in the probability of a moderate or severe lower respiratory symptom.     

A Method for Predicting the Performance of Packed Columns Operating with a Reactive Scrubbing Liquid That Control Gaseous Air Pollutants

Abstract

A method for predicting the performance of packed columns that control gaseous air pollutants has been developed that exploits the advances in both computer software and hardware commonly used by practicing engineers. The solution of the simultaneous partial differential equations that describe the absorption process in packed columns that occurs in the presence of chemical reaction is obtained by converting the partial differential equations to systems of ordinary differential equations. These systems of ordinary differential equations are then solved using the method of lines along with a variable step, variable order numerical method. The method is applicable to systems in which there are multiple reactions within the liquid phase. The reactions can be of any order and can be reversible. The programming is simple and the machine running time is minimal. The method is illustrated here with an example.     

Collaborative Testing of Methods to Measure Air Pollutants II. The Non-Dispersive Infrared Method for Carbon Monoxide

The Methods Standardization Branch of the Environmental Protection Agency, National Environmental Research Center, has undertaken a program to standardize methods used in measuring air pollutants covered by the national primary and secondary air quality standards. This paper presents the results of a collaborative test of the method specified for carbon monoxide.

The test involved analysis of CO in air samples (in cylinders) by participating laboratories. Three concentrations, covering the range of the method which is, 0 to 58 mg/m³, were analyzed dry and humidified on each of three days by 15 collaborators. The method of analysis, nondispersive infrared spectrometry (NDIR), involved an NDIR instrument in combination with different procedures for eliminating water vapor interference. A statistical analysis of the data obtained produced the following results: 1. The checking limit for duplicates (replication error) is 0.5 mg/m³.

2. The repeatability (variation within a laboratory) is 1.6 mg/m³.

3. The reproducibility (variation between laboratories) varies nonlinearly with concentration; i.e., a minimum of 2.3 mg/m³ at a concentration of 20 mg/m³ and ranges as high as 4.3 mg/m³ in the concentration range of 0 to 58 mg/m³.

4. The reproducibility at the level of the national primary ambient air quality standard, 10 mg/m³-8-hour average, is 2.5 mg/m³ or 25%.

5. The minimum detectable sensitivity is estimated to be 0.3 mg/m³.

6. Compensation for water vapor interference is satisfactorily accomplished using drying agents and refrigeration methods. The use of narrow-band optical filters alone may not provide adequate compensation.

7. The accuracy obtained depends upon the availability of reliable calibration gases. Based on the results of this study, the method produces results that average 2.5% high.

Future papers will contain test results for methods to measure other air pollutants.     

Vegetation: A Sink for Atmospheric Pollutants

The possibility of vegetation being an important sink for gaseous air pollutants was investigated. Plant pollutant uptake measurements were made utilizing a typical vegetation canopy and chambers that were designed specifically for gaseous exchange studies. The data indicate that an alfalfa canopy removed gases from the atmosphere in the following order: hydrogen fluoride (HF) > sulfur dioxide (SO₂) > chlorine (Cl₂) > nitrogen dioxide (NO₂) > ozone (O₃) > peroxyacetyl nitrate (PAN) > nitric oxide (NO) > carbon monoxide (CO). The absorption rate of NO was low, and no absorption of CO could be detected with the methods used. In the typical ambient concentration range uptake increased linearly with increasing concentration except for O₃ and Cl₂ which caused partial stomatal closure at the higher concentrations. Wind velocity above the plants, height of the canopy, and light intensity were shown to affect the pollutant removal rate. A relationship between the absorption rate and solubility of the pollutant in water was also shown. It was concluded that vegetation may be an important sink for many gaseous air pollutants.     

Evaluation of Canisters for Measuring Emissions of Volatile Organic Air Pollutants from Hazardous Waste Incineration

Regulation to control air emissions of toxic organic compounds require the collection and analysis of effluent gas from low level sources such as hazardous waste incinerators. The standard SW- 846 Method specifies the use of Tenax and Tenax/charcoal adsorbent traps for collection of volatile organics from incinerators. This study evaluates passivated stainless steel canisters as an alternative to adsorbent traps to eliminate some of the problems associated with adsorbent sampling. Initially the stability of 18 nonpolar, volatile organic compounds was determined in Summa-treated stainless steel canisters with greater than 100 ppmv HCI and saturated with water vapor. All 18 components were stable for a twoweek period; however, an Interference caused a 10-fold increase In the FID response of trlchloroethylene, toluene, and chlorobenzene. No Interference of the ECD response was found for any of the 11 compounds detected with the ECD including trlchloroethylene. A pilot scale incinerator was sampled using canisters, and the destruction efficiency of 1,1,1-trichloroethane was determined at a concentration of less than 0.5 ppbv while determining 1,1-dichloroethylene, the major product of Incomplete combustion, at a concentration of 8000 ppbv from the same sample.     

A Comparative Analysis of Modeled and Monitored Ambient Hazardous Air Pollutants in Texas: A Novel Approach Using Concordance Correlation

Abstract

Often, in studies evaluating the health effects of hazardous air pollutants (HAPs), researchers rely on ambient air levels to estimate exposure. Two potential data sources are modeled estimates from the U.S. Environmental Protection Agency (EPA) Assessment System for Population Exposure Nationwide (ASPEN) and ambient air pollutant measurements from monitoring networks. The goal was to conduct comparisons of modeled and monitored estimates of HAP levels in the state of Texas using traditional approaches and a previously unexploited method, concordance correlation analysis, to better inform decisions regarding agreement. Census tract-level ASPEN estimates and monitoring data for all HAPs throughout Texas, available from the EPA Air Quality System, were obtained for 1990, 1996, and 1999. Monitoring sites were mapped to census tracts using U.S. Census data. Exclusions were applied to restrict the monitored data to measurements collected using a common sampling strategy with minimal missing values over time. Comparisons were made for 28 HAPs in 38 census tracts located primarily in urban areas throughout Texas. For each pollutant and by year of assessment, modeled and monitored air pollutant annual levels were compared using standard methods (i.e., ratios of model-to-monitor annual levels). Concordance correlation analysis was also used, which assesses linearity and agreement while providing a formal method of statistical inference. Forty-eight percent of the median model-to-monitor values fell between 0.5 and 2, whereas only 17% of concordance correlation coefficients were significant and greater than 0.5. On the basis of concordance correlation analysis, the findings indicate there is poorer agreement when compared with the previously applied ad hoc methods to assess comparability between modeled and monitored levels of ambient HAPs.     

A Comparison Study of Various Types of Ozone and Oxidant Detectors Which Are Used for Atmospheric Air Sampling

Four continuous automatic analyzers for measurement of atmospheric levels of ozone were used in a calibration and field study. These were (1) a colorimetric instrument based upon detection of iodine released from neutral potassium iodide reagent, {2) a coulometric instrument utilizing the polarization current as a measurement of iodine released by ozone in a cell contacted by potassium iodide reagent, (8) a galvanic cell measuring bromine release by ozone, and (4) an ultraviolet photometer. Some ozone determinations by the manual rubber cracking procedure were included. After calibration with ozone the average relative response to atmospheric ozone levels for each instrument was determined using the colorimetric oxidant analyzer as an arbitrary standard. These responses ranged from 77 percent for the galvanic cell 90 percent for the photometer. The instrument of choice for any given application would seem to be governed by requirements for precision specificity, portability, reliability, and ease of operation.     

A Method for Using Air Pollution Measurements and Public Opinion to Establish Ambient Air Quality Standards

Air quality was comprehensively evaluated by means of sampling at 21 locations over metropolitan Birmingham during a period of one year. Thousands of integrated samples of three common atmospheric gaseous pollutants and two common particulate pollutants were collected and analyzed. Following the year of sampling in 1964, a random household survey was completed by conducting personal interviews at more than 7200 households over metropolitan Birmingham. Statistical reduction of household survey results by census tract and by neighborhood area provided domestic fuel and waste burning emission data as well as public (resident) opinion on specific air pollution effects. The relationship between ambient air quality and neighborhood opinion of air pollution effects on health and property are evaluated statistically. Ambient standards are suggested which are based upon those air pollution levels shown to have adverse effects on approximately one-third of the people.     

A Method for Determining Source Reduction Required to Meet Air Quality Standards

Governmental boundaries which divide our states frequently do not coincide with the natural geographic and atmospheric conditions affecting regional air pollution problems. Moreover, the control regulations of one state may vary from those of its neighbors. Such areal synthesis of air pollution control measures might only minimally curb the difficulties.

Continuity of control will require cooperation among contiguous states. In this study the attitudes of incumbent elected officials and air pollution experts (both from within the Philadelphia metropolitan area) toward governmental responsiveness have been investigated. It was hypothesized that politicians would want to demonstrate a status quo approach while experts would advocate the creation of an environmental agency for the Philadelphia region’s pollution problems. However, both sample groups responded to the questionnaire survey affirming that they want government to establish an environmental regional control agency, based upon an interstate compact, that has authority strong enough to be a strict enforcing agent. This regional agency should meet all federal conditions and thus receive maximum federal financial assistance. The policy level officials of this agency should be appointed experts—so as to avoid partisan politics, and to acquire the most qualified personnel.     

Black Liquor Oxidation as a Method for Reducing Air Pollution from Sulfate Pulping

This paper will discuss the sources of odorous air pollutants from sulfate pulping operations. One of the major sources is the recovery furnace. Odors from this source can be reduced considerably by oxidation of the black liquor prior to evaporation and burning. The procedure has been used with considerable success in the northwestern and northeastern parts of the United States. Unfortunately, the majority of sulfate pulp production occurs in areas where southern pine is the basic raw material. For several reasons the black liquor resulting from southern pine operations presents problems when the usual oxidation procedures are used. Although not as effective as normal black liquor oxidation strong black liquor can be oxidized without too much difficulty. Various procedures for oxidation of black liquor will be discussed. Results of stack sampling in U. S. pulp mills with and without the oxidation unit in operation will be reported.     

Evaluation of a Test Method for Measuring Indoor Air Emissions from Dry-Process Photocopiers

ABSTRACT

A large chamber test method for measuring indoor air emissions from office equipment was developed, evaluated, and revised based on the initial testing of four dry-process photocopiers. Because all chambers may not necessarily produce similar results (e.g., due to differences in sink effects, temperature and humidity control, air exchange, pollutant monitoring, and measurement biases), a preliminary four-laboratory evaluation of the revised test method was conducted. To minimize variability, the evaluation used a single dry-process photocopier that was shipped to each of the four laboratories along with supplies (i.e., toner and paper).

The results of this preliminary four-laboratory evaluation demonstrate that the test method was used successfully in the different chambers to measure emissions from dry-process photocopiers. Differences in chamber design and construction appeared to have had minimal effect on the results for the volatile organic compounds (VOCs). Perhaps more important than the chamber itself is the sample analysis as identified by duplicate samples that were analyzed by a different laboratory. Percent relative standard deviation (%RSD) was used to provide a simplistic view of interlaboratory precision for this evaluation. Excluding problems with suspected analytical bias observed from one of the laboratories, the precision was excellent for the VOCs with RSDs of less than 10% in most cases. Less precision was observed among the laboratories for aldehydes/ketones (RSD of 23.2% for formaldehyde). The precision for ozone emission rates among three of the laboratories was excellent (RSD of 7.9%), but emission rates measured at the fourth laboratory were much higher.     

A Combustion Method for the Determination of Solvent Vapors at Low Concentrations in Air

The nitrogen-containing products of smog chamber reactions have been the subject of much controversy. Concern has arisen over nitrogen products because of the almost universally poor nitrogen balance reported for irradiated mixtures of hydrocarbons and nitrogen oxides. Some possible nitrogen-containing products, such as molecular nitrogen, nitrous oxide, and nitroolefins have been investigated and shown to be unimportant. The nitrogen products most often measured are peroxyacetyl nitrate and residual nitrogen dioxide. These two products rarely comprise more than 70% of the initial nitrogen at the end of an experiment, and often account for less than 50%. Previous experiments in which total nitrate was determined in the gas phase and on the vessel walls at the end of irradiation have shown very good nitrogen balances. The assumption has been made that the nitrate arises from nitric acid formed on the walls by adsorbed N₂O₅.

In the work reported here, all major nitrogen-containing compounds have been monitored continuously for the first time. Nitric oxide and nitrogen dioxide have been monitored by chemilumines-cence and automated Saltzman techniques. Methyl, ethyl, and peroxyacetyl nitrate have been determined by gas chromatogra-phy. Two methods, one continuous and one integrated, have been specially developed to measure nitric acid both in the smog chambers and in the atmosphere. Continuous determination of these compounds yields good nitrogen balances throughout the irradiations.

Profiles of the nitrogen-containing species from irradiated HC/ NO_x mixtures are discussed in terms of nitrogen products and nitrogen balance. Differences in product distribution for different hydrocarbon systems are also considered. Using rate information from the nitrogen compound profiles, important reactions leading to nitrogen-containing products are identified. Interference with the chemiluminescent technique by HON0₂, PAN, and C₂H₅ONO₂ is discussed.     

A Fast Gas Chromatographic Method for Measuring C2-C6 Alkanes and Alkenes in Air

The Environmental Protection Agency is responsible for establishing, reviewing, and revising standards of performance for new stationary sources of air pollution. Since this federal program was authorized in 1970, standards of performance (commonly referred to as new source performance standards or NSPS) have been developed for 34 categories of stationary sources. These regulations have focused primarily on large new sources of particulate matter, NO _x , and SO₂ emissions. Recently, work has begun on NSPS for a number of source categories that emit volatile organic compounds. Environmental professionals in these industries and in many regulatory agencies have little direct experience with the NSPS program and are unaware of the detailed engineering, cost, and economic information available with each proposed rulemaking. This article, therefore, reviews the purposes, procedures, and benefits of the NSPS program. A summary of the NSPS that have been promulgated through February 1983 are presented in tabular form.