Air Levels and Mutagenicity of PM-10 in an Indoor Ice Arena

Abstract

Hazardous waste sites and industrial facilities contain area sources of fugitive emissions. Emission rate measurements or estimates are necessary for air pathway assessments for these sources. Emission rate data can be useful for the design of emission control and remediation strategies as well as for predictive modeling for population exposure assessments. This paper describes the use of a direct emission measurement approach – the enclosure approach using an emission isolation flux chamber – to measure emission rates of various volatile organic compounds (VOCs) from contaminated soil and water. A variety of flux chamber equipment designs and operating procedures have been employed by various researchers. This paper contains a review of the design and operational variables that affect the accuracy and precision of the method. Guidance is given as to the optimum flux chamber design and operating conditions for various types of emission sources. Also presented is a generic quality control program that gives the minimum number of duplicate, blank, background, and repeat samples that should be performed.     

The Altitude: A Fundamental Parameter in the Use of Air Quality Standards

Organic vapors are emitted to the indoor air from a variety of consumer products and building materials. The U.S. EPA Is evaluating the emission characteristics from such sources using small environmental test chambers. Emission rate data are presented, and the effect of temperature and air exchange rate are discussed. Models are used to account for the Impact of chamber concentration and “wall effects” on emission rates. Indoor concentrations of specific organlcs emitted from a silicone caulk are estimated from the chamber test data.     

Determination of VOC Emission Rates and Compositions for Offset Printing

Abstract

The release rates of volatile organic compounds (VOC) as fugitive emissions from offset printing are difficult to quantify, and the compositions are usually not known. Tests were conducted at three offset printing shops that varied in size and by process. In each case, the building shell served as the test “enclosure,” and air flow and concentration measurements were made at each air entry and exit point. Emission rates and VOC composition were determined during production for (1) a small shop containing three sheetfed presses and two spirit duplicators (36,700 sheets, 47,240 envelopes and letterheads), (2) a medium-size industrial in-house shop with two webfed and three sheetfed presses, and one spirit duplicator (315,130 total sheets), and (3) one print room of a large commercial concern containing three webfed, heatset operations (1.16 x 106 ft) served by catalytic air pollution control devices. Each test consisted of 12 one-hour periods over two days. Air samples were collected simultaneously during each period at 7-14 specified locations within each space. The samples were analyzed by gas chromatography (GC) for total VOC and for 13-19 individual organics. Samples of solvents used at each shop were also analyzed by GC. Average VOC emission rates were 4.7-6.1 kg/day for the small sheetfed printing shop, 0.4-0.9 kg/day for the industrial shop, and 79-82 kg/day for the commercial print room. Emission compositions were similar and included benzene, toluene, xylenes, ethylbenzene, and hexane. Comparison of the emission rates with mass balance estimates based on solvent usage and composition were quite consistent. The average compositions of emissions from these tests were much more detailed than has been previously available, but they agreed well with previous chemical fingerprint values for toluene and o-xylene, which have been successfully applied to source-receptor modeling for graphic arts.     

Emission of biocides from treated materials test procedures for water and air

Methods for the determination of biocide emissions from treated materials into water and air were developed and tested in order to support a comparative ecological assessment of biocidal products. Leaching tests, experiments with simulated rain, extraction cleaning of carpets and emission chamber tests were performed with a series of treated materials. The experiments focused on the effect of changes in the procedure as well as characteristics of the specimens and demonstrate the suitability of the proposed methods for biocides of different product types. It was demonstrated that emissions of biocides into water can be compared on the basis of leaching tests in which the emission kinetics of the active ingredients are recorded. However, the water volume per surface area and the timetable for water changes have to be defined in such tests. Functions of flux rates related to time can be well described for inorganic compounds, whereas modelling of the data is more complicated for organic substances. Emission chamber tests using 20-litre and 23-litre glass exsiccators, originally developed to study volatile organic compounds, were successfully adapted for the investigation of the emission of biocides from treated materials which are usually semi volatile organic compounds. However test parameters and the method of analysis have to be adapted to the substances to be determined. Generally, it was found that the emission curves for the semi volatile organic compounds investigated differ from those of volatile organic compounds.     

Derivation of new emission factors for quantification of mass emissions when using optical gas imaging for detecting leaks

This paper describes the development of new "leak/no-leak" emission factors that are suitable for estimating facilities' fugitive emissions when using an alternative work practice (AWP) that is based on optical gas imaging technology for detecting leaking piping system components. These emission factors were derived for valves, pumps, and connectors/flanges for instrument leak detection thresholds ranging from 3 to 60 g/hr using a combination of field data and Monte Carlo statistical simulation techniques. These newly derived leak/no-leak emission factors are designed to replace the U.S. Environment Protection Agency (EPA) 1995 Protocol factors, which were based on Method 21 monitoring of leaks at "uncontrolled" facilities. The emission factors published in the 1995 Protocol have not been updated since the 1970s. This derivation is based on results where the authors document the use of a Monte Carlo simulation technique to quantify the required leak detection thresholds that provide equal--or better--environmental benefits for an AWP. The use of these newly derived emission factors is demonstrated for different methods of computing fugitive emissions from a hypothetical model refinery. The resulting facility emissions calculated by using these new emission factors is compared with the existing emission estimation methods provided in the EPA 1995 Protocol. The results demonstrate that the new emission factors provide an emission estimate that is the closest to that obtained from the direct determination of total emissions by Monte Carlo simulations.     

Criteria and air-toxic emissions from in-use automobiles in the National Low-Emission Vehicle program

The U.S. Environmental Protection Agency (EPA) implemented a program to identify tailpipe emissions of criteria and air-toxic contaminants from in-use, light-duty low-emission vehicles (LEVs). EPA recruited 25 LEVs in 2002 and measured emissions on a chassis dynamometer using the cold-start urban dynamometer driving schedule of the Federal Test Procedure. The emissions measured included regulated pollutants, particulate matter, speciated hydrocarbon compounds, and carbonyl compounds. The results provided a comparison of emissions from real-world LEVs with emission standards for criteria and air-toxic compounds. Emission measurements indicated that a portion of the in-use fleet tested exceeded standards for the criteria gases. Real-time regulated and speciated hydrocarbon measurements demonstrated that the majority of emissions occurred during the initial phases of the cold-start portion of the urban dynamometer driving schedule. Overall, the study provided updated emission factor data for real-world, in-use operation of LEVs for improved emissions modeling and mobile source inventory development.     

Improvements to lawn and garden equipment emissions estimates for Baltimore, Maryland

Lawn and garden equipment are a significant source of emissions of volatile organic compounds (VOCs) and other pollutants in suburban and urban areas. Emission estimates for this source category are typically prepared using default equipment populations and activity data contained in emissions models such as the U.S. Environmental Protection Agency's (EPA) NONROAD model or the California Air Resources Board's (CARB) OFFROAD model. Although such default data may represent national or state averages, these data are unlikely to reflect regional or local differences in equipment usage patterns because of variations in climate, lot sizes, and other variables. To assess potential errors in lawn and garden equipment emission estimates produced by the NONROAD model and to demonstrate methods that can be used by local planning agencies to improve those emission estimates, this study used bottom-up data collection techniques in the Baltimore metropolitan area to develop local equipment population, activity, and temporal data for lawn and garden equipment in the area. Results of this study show that emission estimates of VOCs, particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO2), and nitrogen oxides (NO(x)) for the Baltimore area that are based on local data collected through surveys of residential and commercial lawn and garden equipment users are 24-56% lower than estimates produced using NONROAD default data, largely because of a difference in equipment populations for high-usage commercial applications. Survey-derived emission estimates of PM and VOCs are 24 and 26% lower than NONROAD default estimates, respectively, whereas survey-derived emission estimates for CO, CO2, and NO(x) are more than 40% lower than NONROAD default estimates. In addition, study results show that the temporal allocation factors applied to residential lawn and garden equipment in the NONROAD model underestimated weekend activity levels by 30% compared with survey-derived temporal profiles.     

Criteria and Air-Toxic Emissions from In-Use Automobiles in the National Low-Emission Vehicle Program

Abstract

The U.S. Environmental Protection Agency (EPA) implemented a program to identify tailpipe emissions of criteria and air-toxic contaminants from in-use, light-duty low-emission vehicles (LEVs). EPA recruited 25 LEVs in 2002 and measured emissions on a chassis dynamometer using the cold-start urban dynamometer driving schedule of the Federal Test Procedure. The emissions measured included regulated pollutants, particulate matter, speciated hydrocarbon compounds, and carbonyl compounds. The results provided a comparison of emissions from real-world LEVs with emission standards for criteria and air-toxic compounds. Emission measurements indicated that a portion of the in-use fleet tested exceeded standards for the criteria gases. Real-time regulated and speciated hydrocarbon measurements demonstrated that the majority of emissions occurred during the initial phases of the cold-start portion of the urban dynamometer driving schedule. Overall, the study provided updated emission factor data for real-world, in-use operation of LEVs for improved emissions modeling and mobile source inventory development.     

Emission factors of air toxics from semiconductor manufacturing in Korea

The development of local, accurate emission factors is very important for the estimation of reliable national emissions and air quality management. For that, this study is performed for pollutants released to the atmosphere with source-specific emission tests from the semiconductor manufacturing industry. The semiconductor manufacturing industry is one of the major sources of air toxics or hazardous air pollutants (HAPs); thus, understanding the emission characteristics of the emission source is a very important factor in the development of a control strategy. However, in Korea, there is a general lack of information available on air emissions from the semiconductor industry. The major emission sources of air toxics examined from the semiconductor manufacturing industry were wet chemical stations, coating applications, gaseous operations, photolithography, and miscellaneous devices in the wafer fabrication and semiconductor packaging processes. In this study, analyses of emission characteristics, and the estimations of emission data and factors for air toxics, such as acids, bases, heavy metals, and volatile organic compounds from the semiconductor manufacturing process have been performed. The concentration of hydrogen chloride from the packaging process was the highest among all of the processes. In addition, the emission factor of total volatile organic compounds (TVOCs) for the packaging process was higher than that of the wafer fabrication process. Emission factors estimated in this study were compared with those of Taiwan for evaluation, and they were found to be of similar level in the case of TVOCs and fluorine compounds.     

Methods to determine response factors for infrared gas imagers used as quantitative measurement devices

Response factors (RF) can be used to characterize relative sensitivity of one compound vs. another compound for the same measurement instrument. Use of RF allows the analysts/operators to calibrate the instrument with one compound and make measurement for a large number of compounds. This method is adopted for Flame Ionization Detector (FID) based survey instruments used in the Leak Detection and Repair (LDAR) practice for control of fugitive emissions of volatile organic compounds. Gas detecting Infrared (IR) cameras have been used for leak detection. However, the RF for IR cameras has not been well established despite some attempt to develop a method for IR camera RF. In addition to a method proposed earlier (Method 1), two new methods for IR camera RF are proposed in this paper: Method 2 based on theoretical approach and Method 3 based on experimental approach. All three methods are examined and compared. Both Methods 2 and 3 have shown the ability to characterize the behavior of RF for various compounds and substantially higher accuracy than Method 1. Method 2 provides a mechanism to generate RF for a large number of compounds without conducting experiments, and is recommended for implementation. The RF derived from this method can be used both in the emerging field of Quantitative Optical Gas Imaging (QOGI) and to answer the most common question that IR camera users ask—whether a particular compound can be imaged by a particular IR camera.Implications: Infrared imager is an efficient tool for detecting gas leaks from process equipment and has been used in leak detection and repair (LDAR) programs for control of fugitive emissions. However, the information regarding which chemical compounds can be imaged and how sensitive a given infrared imager is for various compounds is limited. A theoretical method is presented in this paper that can answer these questions without conducting resource-intensive experiment. The results of this theoretical method has good agreement with experimental data. The method has been used to predict relative sensitivity for 398 compounds.     

Ethanol emission from loose corn silage and exposed silage particles

Silage on dairy farms has been identified as a major source of volatile organic compound (VOC) emissions. However, rates of VOC emission from silage are not accurately known. In this work, we measured ethanol (a dominant silage VOC) emission from loose corn silage and exposed corn silage particles using wind tunnel systems. Flux of ethanol was highest immediately after exposing loose silage samples to moving air (as high as 220 g m^?2 h^?1) and declined by as much as 76-fold over 12 h as ethanol was depleted from samples. Emission rate and cumulative 12 h emission increased with temperature, silage permeability, exposed surface area, and air velocity over silage samples. These responses suggest that VOC emission from silage on farms is sensitive to climate and management practices. Ethanol emission rates from loose silage were generally higher than previous estimates of total VOC emission rates from silage and mixed feed. For 15 cm deep loose samples, mean cumulative emission was as high as 170 g m^?2 (80% of initial ethanol mass) after 12 h of exposure to an air velocity of 5 m s^?1. Emission rates measured with an emission isolation flux chamber were lower than rates measured in a wind tunnel and in an open setting. Results show that the US EPA emission isolation flux chamber method is not appropriate for estimating VOC emission rates from silage in the field.     

Emission Factors of Air Toxics from Semiconductor Manufacturing in Korea

Abstract

The development of local, accurate emission factors is very important for the estimation of reliable national emissions and air quality management. For that, this study is performed for pollutants released to the atmosphere with source-specific emission tests from the semiconductor manufacturing industry. The semiconductor manufacturing industry is one of the major sources of air toxics or hazardous air pollutants (HAPs); thus, understanding the emission characteristics of the emission source is a very important factor in the development of a control strategy. However, in Korea, there is a general lack of information available on air emissions from the semiconductor industry. The major emission sources of air toxics examined from the semiconductor manufacturing industry were wet chemical stations, coating applications, gaseous operations, photolithography, and miscellaneous devices in the wafer fabrication and semiconductor packaging processes. In this study, analyses of emission characteristics, and the estimations of emission data and factors for air toxics, such as acids, bases, heavy metals, and volatile organic compounds from the semiconductor manufacturing process have been performed. The concentration of hydrogen chloride from the packaging process was the highest among all of the processes. In addition, the emission factor of total volatile organic compounds (TVOCs) for the packaging process was higher than that of the wafer fabrication process. Emission factors estimated in this study were compared with those of Taiwan for evaluation, and they were found to be of similar level in the case of TVOCs and fluorine compounds.     

Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

Nonvolatile,semivolatile, or volatile: Redefining volatile for volatile organic compounds

Although widely used in air quality regulatory frameworks, the term “volatile organic compound” (VOC) is poorly defined. Numerous standardized tests are currently used in regulations to determine VOC content (and thus volatility), but in many cases the tests do not agree with each other, nor do they always accurately represent actual evaporation rates under ambient conditions. The parameters (time, temperature, reference material, column polarity, etc.) used in the definitions and the associated test methods were created without a significant evaluation of volatilization characteristics in real world settings. Not only do these differences lead to varying VOC content results, but occasionally they conflict with one another. An ambient evaporation study of selected compounds and a few formulated products was conducted and the results were compared to several current VOC test methodologies: SCAQMD Method 313 (M313), ASTM Standard Test Method E 1868-10 (E1868), and U.S. EPA Reference Method 24 (M24). The ambient evaporation study showed a definite distinction between nonvolatile, semivolatile, and volatile compounds. Some low vapor pressure (LVP) solvents, currently considered exempt as VOCs by some methods, volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents they are meant to replace. Conversely, bio-based and heavy hydrocarbons did not readily volatilize, though they often are calculated as VOCs in some traditional test methods. The study suggests that regulatory standards should be reevaluated to more accurately reflect real-world emission from the use of VOC containing products.

Implications:The definition of VOC in current test methods may lead to regulations that exclude otherwise viable alternatives or allow substitutions of chemicals that may limit the environmental benefits sought in the regulation. A study was conducted to examine volatility of several compounds and a few formulated products under several current VOC test methodologies and ambient evaporation. This paper provides ample evidence to warrant a reevaluation of regulatory standards and provides a framework for progressive developments based on reasonable and scientifically justifiable definitions of VOCs.     

Interlaboratory Study of a Test Method Measuring Total Volatile Organic Compound Content of Consumer Products

Abstract

Consumer products are potentially significant sources of volatile organic compounds (VOCs), which are precursors to the formation of ozone in photochemical smog. To address the problem of ozone formation in ambient air, the U.S. Environmental Protection Agency (EPA) has been involved in the development of test methods for measuring the VOC content of consumer products. This paper describes results of an interlaboratory study to estimate the repeatability (precision of analyses performed by a single laboratory) and reproducibility (precision of analyses performed by different laboratories) of the consumer products’ VOC measurement method based on EPA Method 24 (for VOCs in surface coatings).

The mean method repeatability was 2.7 wt % VOC, and the mean method reproducibility was 4.8 wt % VOC. Method repeatability ranged from 0.2 to 4.4 wt % VOC, and reproducibility ranged from 0.6 to 11.9 weight percent VOC. The precision of the VOC method for consumer

products is similar to the precision of EPA Method 24 for surface coatings.     

Fate and Transport of Fuel Components Below Slightly Leaking Underground Storage Tanks

Fuel leaks from underground storage tanks (USTs) and piping have been a major source of groundwater contamination. In the U.S. and Europe, regulations requiring upgrading of USTs to meet specific standards have significantly reduced instances of fuel contamination. Leak detection is primarily dependent on physical measurement systems that are generally capable of detecting leak rates as small as 0.2 L/h. Fuel leaks that are smaller than this detection threshold may remain undetected for long periods of time, posing a risk of contamination to shallow groundwater resources in sensitive areas. This risk was evaluated by modeling fate and transport of fuel components from small UST leaks under a variety of subsurface conditions and assuming that secondary containment does not exist. It was found that small leaks do have the potential to impact shallow groundwater, particularly if subsurface conditions are not conducive to natural attenuation processes. This may explain situations where groundwater contamination has been found below service stations in virgin areas that have upgraded leak detection systems. Modeling indicates that passive venting of tank and piping backfill could virtually eliminate the volatile components of fuel resulting from small leaks. Monitoring the tank and piping backfill for persistent gasoline vapor under very low vapor extraction conditions may be the best way to detect small chronic fuel leaks. Routine monitoring of shallow groundwater should be a component of a leak detection program, particularly in high-risk areas.     

Transient analysis of volatile organic compound concentrations for estimating emission rates

While emission rates of volatile organic compounds (VOCs) have been obtained for building materials, furnishings and processes in chambers, field measurements are more difficult. Procedures to estimate emission rates using transient analysis of VOC concentrations are described and applied in a two-story classroom/office building. The analysis employs semi-real-time VOC concentrations determined with a portable GC/FID and simultaneous air change rate measurements using tracer gas decay. The results of the analysis yield consistent values of emission rates for building materials ranging from 0.20 to 0.40 mg m⁻² h⁻¹ when normalized by floor area. Occupancy-related emissions were more difficult to estimate and covered a wider range from roughly 0.1 to 1.5 mg m⁻² h⁻¹. The test data were also analyzed in an attempt to determine sink parameters, but these efforts were not particularly successful. Furthermore, in these tests, the inclusion of sink effects did not significantly impact the estimated emission rates. While this paper offers a transient analysis approach that may lead to improved field estimates of VOC emission rates, it is not presented as a definitive methodology. Nevertheless, transient analysis has potential for use in other buildings, but simultaneous air change rate measurements are critical in its application in estimating VOC emission rates in the field.     

Informative Report

Abstract

Chemical composition and particle size data for particulate emissions from stationary sources are required for environmental health effect assessments, air chemistry studies and for air quality modeling investigations such as source apportionment. The Information presented In this paper is directed to those individuals concerned with these environmental Investigations. In this study, particulate emissions from a group of non-ferrous smelters have been physically and chemically characterized. Emission samples were collected at the baghouse outlets from smelter furnaces and at smelter acid plant stacks at three locations; a zinc, a lead, and a copper smelter.

Mass emission rate determinations were made by EPA reference methods. Cascade impactors were used to collect in-stack samples for particle size distribution measurements. Particulate samples for chemical characterization were collected on membrane filters for analysis by X-ray fluorescence spectroscopy. Development of measurement techniques required to determine the elemental composition of the total mass and sized fractions of the emission are discussed. Results of the tests at the three smelters include total mass and elemental emission rates, particle size distribution, and the elemental composition of the total particulate mass and of sized fractions from both the smelter furnaces and acid plants. The results obtained at the copper smelter may not be representative of the emissions at the many copper smelters where reverbatory furnaces have been replaced.