The Need for Representative Ambient Air Carbon Monoxide Sampling

Recent investigations have indicated that ambient air CO measurements may not reflect population exposure to CO. The lack of correlation may be due to improper siting of CO instruments, improper interpretation of air quality data, or both. Studies of population carboxy-hemoglobin levels are evaluated and compared with ambient air data.,

No significant correlation was found between median population COHb levels and reductions in CO concentrations required to meet ambient air standards when calculations used to estimate reductions were based on the second highest 8 hour average. However, calculated reductions based on annual average concentrations and a trend analysis technique correlated significantly with COHb levels in five cities from which both CAMP and COHb data were available.

Studies to determine the nature of the relationship between ambient air CO concentrations and population COHb levels are needed. The differences between the Occupational Safety and Health Act Regulations and the National Ambient Air Standards for carbon monoxide should be scrutinized to determine if a redefinition of the standards or their applicability is warranted. A reevaluation of the controls necessary to make reductions in population COHb burden may be necessary.     

Ambient Carbon Monoxide And Its Fate in the Atmosphere

Carbon monoxide, the most abundant air pollutant found in the atmosphere generally exceeds that of all other pollutants combined (excluding C0₂). An estimated tonnage of >87 X 10⁶ of CO was emitted in the United States from major technological sources alone during 1966. More than 90% of the total CO emitted from fossil fuels is derived from gasoline powered motor vehicles. Other sources of CO include emissions from coal and fuel oil burning, aircraft and open burning. Some CO is also formed by certain vegetation and marine invertebrates (siphonophores). Chemical reactions of CO in the upper and lower atmosphere are discussed. Chemical oxidation of CO in the lower atmosphere by molecular oxygen is very slow. The exact duration of CO in the lower atmosphere is not known with certainty; however, the mean residence time has been variously estimated to be between 0.3 and 5.0 years. In the absence of scavenging processes the estimated world-wide CO emission would be sufficient to raise the’atmospheric level by 0.03 ppm per year, yet the background levels of CO in clean air do not appear to be increasing. Several potential sinks are discussed. Knowledge of the mechanism of process of removal of CO from the lower atmosphere is unsatisfactory; the process, at the present time, cannot be identified with certainty.     

Ambient Air Monitoring for Sulfur Compounds

The role of sulfur compounds in our environment has been the subject of much speculation during the past two decades. An evaluation of the effect of man-made contributions to the biogeochemical sulfur cycle requires a comprehensive examination of source magnitudes, atmospheric concentrations and removal processes. Many voids exist in our present knowledge of these parameters despite the contributions of numerous researchers. Adequate information is needed concerning the various forms of sulfur as well as other critical constituents which exist in our biosphere so that their interrelationship and role in the mechanisms of the sulfur cycle may be more fully understood.     

The Association between Ambient Carbon Monoxide Levels and Daily Mortality in Toronto,Canada

ABSTRACT

The role of ambient levels of carbon monoxide (CO) in the exacerbation of heart problems in individuals with both cardiac and other diseases was examined by comparing daily variations in CO levels and daily fluctuations in nonaccidental mortality in metropolitan Toronto for the 15-year period 1980–1994. After adjusting the mortality time series for day-of-the-week effects, nonparametic smoothed functions of day of study and weather variables, statistically significant positive associations were observed between daily fluctuations in mortality and ambient levels of carbon monoxide, nitrogen dioxide, sulfur dioxide, coefficient of haze, total suspended particulate matter, sulfates, and estimated PM_2.5 and PM₁₀. However, the effects of this complex mixture of air pollutants could be almost completely explained by the levels of CO and total suspended particulates (TSP). Of the 40 daily nonaccidental deaths in metropolitan Toronto, 4.7% (95% confidence interval of 3.4%–6.1%) could be attributable to CO while TSP contributed an additional 1.0% (95% confidence interval of 0.2–1.9%), based on changes in CO and TSP equivalent to their average concentrations. Statistically significant positive associations were observed between CO and mortality in all seasons, age, and disease groupings examined. Carbon monoxide should be considered as a potential public health risk to urban populations at current ambient exposure levels.     

The Effect of Reformulated Gasoline on Ambient Carbon Monoxide Concentrations in Southeastern Wisconsin

Abstract

Reformulated gasoline (RFG) contains oxygen additives such as methyl tertiary butyl ether or ethanol. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of carbon monoxide (CO) and volatile organic compounds (VOCs). Because VOCs react with sunlight to form ozone (O₃), the Clean Air Act requires severe O₃ nonattainment areas such as southeastern Wisconsin to use RFG. On July 17, 2001, the U.S. Environmental Protection Agency (EPA) granted Milwaukee, WI, and Chicago, IL, a waiver from the VOC reduction requirement of Phase II RFG. The VOC reduction requirement was lowered from 27.4% of the 1990 baseline fuel to 25.4%. The assumption was that ethanol-blended RFG would lower summertime CO concentrations sufficiently to offset the increased VOC emissions. The waiver is estimated to increase VOC emissions by ～0.8%, or 0.4 t of VOC on a hot summer weekday. This study evaluates whether RFG has been effective in lowering southeastern Wisconsin ambient CO concentrations. Three years of ambient CO data before RFG was introduced were compared with the first three years of ambient CO data after RFG was introduced. This paper also evaluates how the meteorology, vehicle inspection/maintenance program, vehicle miles traveled, and stationary source emissions influence CO concentrations. The winter decrease in ambient CO concentrations was found to be statistically significant, while the summer data showed no statistically significant change, indicating that RFG is most effective lowering ambient CO concentrations in cold weather.     

A Survey Technique for Determining The Representativeness of Urban Air Monitoring Stations With Respect to Carbon Monoxide

An air quality survey technique for measuring the horizontal spatial variation of carbon monoxide concentrations in urban areas is described; it was used to determine how representative an urban air monitoring station is of concentrations throughout the city.

The survey technique was applied in San Jose, Calif., where 1128 samples were collected over a six-month period and were compared with the values recorded simultaneously at the urban air monitoring station. All samples were collected at “breathing height” within a 13-square-mile grid which included the downtown area as well as surrounding residential and industrial locations. Three basic sampling strategies were employed to answer specific questions about the distribution of carbon monoxide concentration: (7) walking sampling, in which samples were obtained while walking along the sidewalks of congested downtown streets, (2) random spatial sampling, in which samples were collected at randomly selected points in the urban grid, and (3) specialized sampling in the immediate vicinity of the air monitoring station.

The results indicate that pedestrians on downtown streets in San Jose can be exposed to concentrations above the federal air quality standards without these values being observed at the air monitoring station. There also is evidence that, at any instant of time, similar values of carbon monoxide exist throughout this city (within a 13-square mile area), provided that measurements are not made in close proximity to streets. Furthermore, the higher concentrations observed in the immediate vicinity of streets decrease quite rapidly with increasing horizontal distance from these streets.

These findings, in the view of the authors, raise serious doubts as to whether it is possible to determine if air quality standards as currently defined are actually being met in urban areas using data from present-day air monitoring stations.     

The Nonlinearity and Related Band Strength of Carbon Monoxide When Applied in Ambient Air Measurement Using Open Long-Path Fourier Transform Infrared Spectrometry

ABSTRACT

The accuracy of CO concentration determination by open-path Fourier transform infrared (FTIR) spectrometry has been re-evaluated in detail. The evaluation focuses on the correction of the calibration curve—the integrated intensity of a standard spectrum—that is used as a comparison spectrum when doing quantitative analysis of CO. Results show that the calibration curve (with 0.5 cm^-1 or 1 cm^-1 resolution) is apparently inclined to be nonlinear under standard conditions, and that the threshold point of nonlinearity is ~0.1 atm-cm. Two commercial FTIR field monitoring systems have been used to investigate the nonlinearity trend. The experimental method consists of using open-path FTIR systems in combination with nondispersive infrared (NDIR) monitors to establish the calibration curve in a semi-closed corridor. The results have been double-checked using closed-cell dynamic equilibrium systems.

When the optical density is larger than a certain value, the curves begin to bend, and when the optical density approaches zero, the band strength is around 178 ± 3 atm^-1 cm^-2 and 173 ± 2 atm^-1 cm^-2, respectively, for 0.5 and 1 cm^-1 resolution at standard temperature and pressure (STP). These values are quite different from other published data that have been acquired by the pressurized method or by high-resolution     

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.     

从空气中捕集CO_2的研究现状

从空气中捕集CO2是一项有前途的新CO2减排技术,具有传统CO2减排技术所没有的多项优势。文中首先介绍了从空气中捕集CO2的意义、可行性、吸收剂选择和捕集器设计原则;然后介绍了最新的原型设计及成本预计;最后讨论了该技术的现存问题和对其他技术的启发。     

Sampling Frequency Guidance for Ambient Air Toxics Monitoring

Abstract

The U.S. Environmental Protection Agency (EPA) is in the process of designing a national network to monitor hazardous air pollutants (HAPs), also known as air toxics. The purposes of the expanded monitoring are to (1) characterize ambient concentrations in representative areas; (2) provide data to support and evaluate dispersion and receptor models; and (3) establish trends and evaluate the effectiveness of HAP emission reduction strategies. Existing air toxics data, in the form of an archive compiled by EPA’s Office of Air Quality Planning and Standards (OAQPS), are used in this paper to examine the relationship between estimated annual average (AA) HAP concentrations and their associated variability. The goal is to assess the accuracy, or bias and precision, with which the AA can be estimated as a function of ambient concentration levels and sampling frequency. The results suggest that, for several air toxics, a sampling schedule of 1 in 3 days (1:3) or 1:6 days may be appropriate for meeting some of the general objectives of the national network, with the more intense sampling rate being recommended for areas expected to exhibit relatively high ambient levels.     

Monitoring of Benzene in Ambient Air with Organic Vapor Badges

The original Texas Intersection Model (TEXIN) for air quality near street intersections has been widely adopted across the nation. At the request of transportation agencies from several states, the TEXIN model was revised to improve its performance and flexibility. The new capabilities include T-intersections, one-way streets, four-way stops, inspection/maintenance capabilities, anti-tampering programs and a short-cut emissions algorithm. TEXIN2 uses the CMA procedures for estimating traffic flow parameters, MOBILE3 to determine free flowing traffic cruise emissions, and CALINE3 to model the pollutant distribution downwind of an intersection. The new model, TEXIN2, offers the user more accurate simulations with enhanced versatility while still requiring a minimal amount of input data.     

Epidemiological Bases for Possible Air Quality Criteria for Carbon Monoxide

Exposures to adequate environmental levels of CO will increase COHb concentrations in human subjects. The amount of this increase is reasonably predictable, and must be considered in relation to exposure to CO in inhaled cigarette smoke as well as to occupational and domestic exposures. The increase in body COHb will result in some degree of impairment of tissue oxygenation.

Methods for estimating COHb levels in large populations are relatively simple. The assumption that an exposure to 30 ppm CO for eight hours will produce on the average, an increase in COHb of 5%, has been substantiated by available data.

Exposure for five hours to between 10 and 12 ppm of CO has been shown to increase the COHb levels in nonsmokers by at least 0.5%. Such an increase adds appreciably to the body burden of COHb in those who do not already have such a body burden from cigarette smoking. Longer exposures could have produced a somewhat greater increase.

Apart from increases in COHb, three possible effects have been a source of major consideration in epidemiologic studies. The first is the production of some persistent toxic reaction. This possibility has been examined with respect to occupational exposure, and the evidence for the occurrence of such a condition is insufficient.

The possible contribution of ambient community CO exposure to the mortality of persons hospitalized with myocardial infarction has been investigated. The evidence suggests that daily average CO values in excess of about 10 ppm may be associated with an increase in mortality in hospitalized patients with myocardial infarction. Substantiation of this impression will require a study of the prognosis of myocardial infarction patients in relationship to COHb levels measured at admission to the hospital.

Finally, in two studies, persons driving motor vehicles which were involved in accidents had higher COHb levels than "control" populations. Controls were not ideal, however. Possible mechanisms by which CO might affect the ability to drive a motor vehicle is suggested in the available data on CO effects upon visual sensitivity, psychological test performance and accurate estimation of time intervals. As little as 2 percent COHb can produce these effects in laboratory studies, and the available epidemiologic information confirms that such an increase in COHb levels among drivers might influence the frequency of accidents.

Specific areas where research is indicated to clarify uncertainties relating to health effects of CO are: 1. The increment in COHb which can be produced by exposures to an average of 20 ppm CO for an eight hour period and the increment which can be produced by 15 ppm for such a period and by 10 ppm for up to twenty-four hours.

2. The relationship of ambient CO levels and of COHb levels to the survival of hospitalized patients with myocardial infarction.

3. The prognostic significance with respect to cardiovascular conditions of elevated levels of COHb.

4. The relationship, if any, between ambient CO and COHb levels and the occurrence of motor vehicle accidents when weather and driving conditions, cigarette smoking, alcohol and drug use, and other factors are adjusted and controlled.

     

An Upper Limit Analysis of Carbon Monoxide Monitoring in the United States

In performing carbon monoxide (CO) studies, the question is invariably raised as to whether available monitoring data are truly representative of the highest ambient 8-hr average CO levels experienced in major cities. The most practical means for such a determinate is to inventory the critical characteristics of monitor siting. The authors catalogued such data for the worst station in eight of the 12 counties measuring the highest number of CO violations in the nation.     

Continuous Determination of Carbon Monoxide and Hydrocarbons in Air by a Modified Infrared Analyzer

The original goals of this project¹ were to establish the shape of a smoke curve for fine suspended particulates in New York City comparable to the International Smoke Curve used in British and other European practice, and to relate two commonly used reporting units of surface concentration, μg/m³ (European practice) and Coh/1000 lineal feet (United States practice), to each other. While not directly a goal of the project, it was essential in the course of work to study the relationship between particulate density readings taken for one hour and two hour sampling periods. Progress toward achievement of these goals is presented in the following pages.     

Carbon Monoxide in the Atmosphere

A carbon monoxide analyzer has been developed which is capable of continuous measurement of the carbon monoxide concentration in the atmosphere. The operating principle of the instrument is the reaction of carbon monoxide with hot mercuric oxide followed by the photometric determination of the mercury vapor produced. Oxygenated hydrocarbons and olefins are quantitatively detected. Those normally present are in the ambient atmosphere in low concentrations relative to CO. Hydrogen and methane in the atmosphere do not interfere with the CO analysis. Measurements of atmospheric CO concentrations in California, Greenland, and Oregon seem to indicate that CO content is an air mass characteristic. North Pacific marine air mass concentrations may be as low as about 0.040 parts per million (ppm) CO, while the air mass over continental California seems to be characterized by CO levels of 0.5-1.0 ppm or greater.     

Toxicological Appraisal of Carbon Monoxide

The draft Technical Report on Air Quality Criteria for Carbon Monoxide shows thorough familiarity with the relevant toxicological studies. The authors selected materials for discussion very judiciously. They present the pertinent information in sufficient detail to permit an independent judgment of its significance, in most instances. The conclusions are firmly based on the information which is presented.     

The National Ambient Air Monitoring Strategy: Rethinking the Role of National Networks

Abstract

A current re-engineering of the United States routine ambient monitoring networks intended to improve the balance in addressing both regulatory and scientific objectives is addressed in this paper. Key attributes of these network modifications include the addition of collocated instruments to produce multiple pollutant characterizations across a range of representative urban and rural locations in a new network referred to as the National Core Monitoring Network (NCore). The NCore parameters include carbon monoxide (CO), sulfur dioxide (SO₂), reactive nitrogen (NO_y), ozone (O₃), and ammonia (NH₃) gases and the major fine particulate matter (PM_2.5) aerosol components (ions, elemental and organic carbon fractions, and trace metals). The addition of trace gas instruments, deployed at existing chemical speciation sites and designed to capture concentrations well below levels of national air quality standards, is intended to support both long-term epidemiological studies and regional-scale air quality model evaluation. In addition to designing the multiple pollutant NCore network, steps were taken to assess the current networks on the basis of spatial coverage and redundancy criteria, and mechanisms were developed to facilitate incorporation of continuously operating particulate matter instruments.     

Exposure of Drivers to Carbon Monoxide

Eleven new cars were driven around a 35 km route comprising heavily trafficked roads in and around London, and the concentrations of carbon monoxide inside and immediately outside the vehicles were continuously monitored. Average levels of CO between 12 and 60 parts per million were found inside the cars, and these levels were between 30 and 80% of the external concentrations. The internal levels varied according to external changes but the changes were greatly damped by the buffering effect of the ventilation system. Differences in internal CO levels were more marked between vehicles than for different runs in the same vehicle and were probably due to differences in the ventilation systems.

Blood carboxy-hemoglobin concentrations which would arise from the CO exposures were calculated. Published data suggest that carboxy-hemoglobin concentrations within the range found (1.5-3.0%) would not be expected to produce an adverse effect on health; there are conflicting views as to whether driving performance would be impaired.