Uncertainties in the current knowledge of some atmospheric trace gases associated with U.S. agriculture: a review

Approximately 80 different crop species are grown in the United States in widely differing geographic areas, climatic and edaphic conditions, and management practices. Although the majority of cultivated acreage in the United States is planted with only about 10 primary crops, uncertainties associated with trace gas emissions arise from: (1) limited data availability, (2) inaccurate estimates because of large temporal and spatial variability in trace gas composition and magnitude of trace gas emissions from agricultural activities, (3) differing characteristics of pollutant emissions from highly dispersed animal feed-lots, and (4) limited understanding of the emissions of semi-volatile organic compounds (SVOCs) associated with agriculture. Although emission issues are of concern, so also is atmospheric deposition to cropping systems, including wet and dry nitrogen, minerals, and organic compounds. These can have feedback effects on trace gas emissions. Overall, the many gaps in our understanding of these aspects of agricultural systems deserve serious attention.     

Emissions from oil and gas operations in the United States and their air quality implications

The energy supply infrastructure in the United States has been changing dramatically over the past decade. Increased production of oil and natural gas, particularly from shale resources using horizontal drilling and hydraulic fracturing, made the United States the world’s largest producer of oil and natural gas in 2014. This review examines air quality impacts, specifically, changes in greenhouse gas, criteria air pollutant, and air toxics emissions from oil and gas production activities that are a result of these changes in energy supplies and use. National emission inventories indicate that volatile organic compound (VOC) and nitrogen oxide (NO_x) emissions from oil and gas supply chains in the United States have been increasing significantly, whereas emission inventories for greenhouse gases have seen slight declines over the past decade. These emission inventories are based on counts of equipment and operational activities (activity factors), multiplied by average emission factors, and therefore are subject to uncertainties in these factors. Although uncertainties associated with activity data and missing emission source types can be significant, multiple recent measurement studies indicate that the greatest uncertainties are associated with emission factors. In many source categories, small groups of devices or sites, referred to as super-emitters, contribute a large fraction of emissions. When super-emitters are accounted for, multiple measurement approaches, at multiple scales, produce similar results for estimated emissions. Challenges moving forward include identifying super-emitters and reducing their emission magnitudes. Work done to date suggests that both equipment malfunction and operational practices can be important. Finally, although most of this review focuses on emissions from energy supply infrastructures, the regional air quality implications of some coupled energy production and use scenarios are examined. These case studies suggest that both energy production and use should be considered in assessing air quality implications of changes in energy infrastructures, and that impacts are likely to vary among regions.

Implications: The energy supply infrastructure in the United States has been changing dramatically over the past decade, leading to changes in emissions from oil and natural gas supply chain sources. In many source categories along these supply chains, small groups of devices or sites, referred to as super-emitters, contribute a large fraction of emissions. Effective emission reductions will require technologies for both identifying super-emitters and reducing their emission magnitudes.     

Modeling to Evaluate Contribution of Oil and Gas Emissions to Air Pollution

Oil and gas production in the Western United States has increased considerably over the past 10 years. While many of the still limited oil and gas impact assessments have focused on potential human health impacts, the typically remote locations of production in the Intermountain West suggests that the impacts of oil and gas production on national parks and wilderness areas (Class I and II areas) could also be important. To evaluate this, we utilize the Comprehensive Air quality Model with Extensions (CAMx) with a year-long modeling episode representing the best available representation of 2011 meteorology and emissions for the Western United States. The model inputs for the 2011 episodes were generated as part of the Three State Air Quality Study (3SAQS). The study includes a detailed assessment of oil and gas (O&G) emissions in Western States. The year-long modeling episode was run both with and without emissions from O&G production. The difference between these two runs provides an estimate of the contribution of the O&G production to air quality. These data were used to assess the contribution of O&G to the 8 hour average ozone concentrations, daily and annual fine particulate concentrations, annual nitrogen deposition totals and visibility in the modeling domain. We present the results for the Class I and II areas in the Western United States. Modeling results suggest that emissions from O&G activity are having a negative impact on air quality and ecosystem health in our National Parks and Class I areas.

Implications: In this research, we use a modeling framework developed for oil and gas evaluation in the western United States to determine the modeled impacts of emissions associated with oil and gas production on air pollution metrics. We show that oil and gas production may have a significant negative impact on air quality and ecosystem health in some national parks and other Class I areas in the western United States. Our findings are of particular interest to federal land managers as well as regulators in states heavy in oil and gas production as they consider control strategies to reduce the impact of development.     

Air quality and its possible impacts on the terrestrial ecosystems of the North American Great Plains: an overview

Over the past several decades, numerous studies have been conducted on the impacts of air pollutants (air quality) on terrestrial ecosystems (crops and forests). Although ambient air is always composed of pollutant mixtures, in determining the relative air quality and its ecosystem impacts at a given geographic location and time, a predominant number of studies have shown that at the present time surface-level O(3) is the most important phytotoxic air pollutant. Within the North American Great Plains, the precursors for surface-level O(3) are mainly anthropogenic NO(x) and VOCs (volatile organic compounds). Texas and Alberta are the top regions of such emissions in the United States and Canada, respectively. This appears to be due mainly to the prevalence of natural gas and/or oil industry in the two regions and the consequent urbanization. Nevertheless, the total emissions of NO(x) and VOCs within the North American Great Plains represent only about 25-36% of the corresponding total emissions within the contiguous United States and the whole of Canada. Within the Great Plains many major crop and tree species are known to be sensitive to O(3). This sensitivity assessment, however, is based mainly on our knowledge from univariate (O(3) only) exposure-plant response studies. In the context of global climate change, in almost all similar univariate studies, elevated CO(2) concentrations have produced increases in plant biomass (both crop and tree species). The question remains as to whether this stimulation will offset any adverse effects of elevated surface O(3) concentrations. Future research must address this important issue both for the Great Plains and for all other geographic locations, taking into consideration spatial and temporal variabilities in the ambient concentrations of the two trace gases.     

Methods of characterizing the distribution of exhaust emissions from light-duty, gasoline-powered motor vehicles in the U.S. fleet

Mobile sources significantly contribute to ambient concentrations of airborne particulate matter (PM). Source apportionment studies for PM10 (PM < or = 10 microm in aerodynamic diameter) and PM2.5 (PM < or = 2.5 microm in aerodynamic diameter) indicate that mobile sources can be responsible for over half of the ambient PM measured in an urban area. Recent source apportionment studies attempted to differentiate between contributions from gasoline and diesel motor vehicle combustion. Several source apportionment studies conducted in the United States suggested that gasoline combustion from mobile sources contributed more to ambient PM than diesel combustion. However, existing emission inventories for the United States indicated that diesels contribute more than gasoline vehicles to ambient PM concentrations. A comprehensive testing program was initiated in the Kansas City metropolitan area to measure PM emissions in the light-duty, gasoline-powered, on-road mobile source fleet to provide data for PM inventory and emissions modeling. The vehicle recruitment design produced a sample that could represent the regional fleet, and by extension, the national fleet. All vehicles were recruited from a stratified sample on the basis of vehicle class (car, truck) and model-year group. The pool of available vehicles was drawn primarily from a sample of vehicle owners designed to represent the selected demographic and geographic characteristics of the Kansas City population. Emissions testing utilized a portable, light-duty chassis dynamometer with vehicles tested using the LA-92 driving cycle, on-board emissions measurement systems, and remote sensing devices. Particulate mass emissions were the focus of the study, with continuous and integrated samples collected. In addition, sample analyses included criteria gases (carbon monoxide, carbon dioxide, nitric oxide/nitrogen dioxide, hydrocarbons), air toxics (speciated volatile organic compounds), and PM constituents (elemental/organic carbon, metals, semi-volatile organic compounds). Results indicated that PM emissions from the in-use fleet varied by up to 3 orders of magnitude, with emissions generally increasing for older model-year vehicles. The study also identified a strong influence of ambient temperature on vehicle PM mass emissions, with rates increasing with decreasing temperatures.     

Determination of Motor Vehicle Profiles for Non-Methane Organic Compounds in the Mexico City Metropolitan Area

ABSTRACT

Non-methane organic compound (NMOC) profiles for on-road motor vehicle emissions were measured in a downtown tunnel and parking garages in Mexico City during 1996. Hydrocarbon samples from the tunnel and ambient air samples (C2-C12) were collected using stainless steel canisters, and carbonyl compounds were collected using 2,4-dinitrophenylhydrazine (DNPH) impregnated cartridges. Canister samples were analyzed by gas chromatog-raphy/flame ionization detection (GC/FID) to ascertain detailed hydrocarbon composition. DNPH samples were analyzed by high performance liquid chromatography (HPLC). NMOC source profiles were quantified for evaporative emissions from refueling, cold start, and hot soak, and on-road operating conditions. The ultimate purpose will be to determine the apportionment of ambient NMOC concentrations using the Chemical Mass Balance (CMB) model. The tunnel profile contained 42.3 ppbC% of alkanes, 20.6 ppbC% of unsaturated compounds, and 22.4 ppbC% of aromatics. The most abundant species were acetylene with 7.22 ppbC%, followed by ipentane with 5.69 ppbC%, and toluene with 5.42 ppbC%. These results were compared with those from studies in the United States. The cold start profile was found to be similar to the tunnel profile, although there were differences in the content of acetylene, isopentane, and oxygenates. The abundance of saturated NMOC in the hot soak profile was similar to gasoline head space profiles; it was also much larger than saturated NMOC in the roadway profile.     

Wildfire and prescribed burning impacts on air quality in the United States

ABSTRACT

Air quality impacts from wildfires have been dramatic in recent years, with millions of people exposed to elevated and sometimes hazardous fine particulate matter (PM _2.5 ) concentrations for extended periods. Fires emit particulate matter (PM) and gaseous compounds that can negatively impact human health and reduce visibility. While the overall trend in U.S. air quality has been improving for decades, largely due to implementation of the Clean Air Act, seasonal wildfires threaten to undo this in some regions of the United States. Our understanding of the health effects of smoke is growing with regard to respiratory and cardiovascular consequences and mortality. The costs of these health outcomes can exceed the billions already spent on wildfire suppression. In this critical review, we examine each of the processes that influence wildland fires and the effects of fires, including the natural role of wildland fire, forest management, ignitions, emissions, transport, chemistry, and human health impacts. We highlight key data gaps and examine the complexity and scope and scale of fire occurrence, estimated emissions, and resulting effects on regional air quality across the United States. The goal is to clarify which areas are well understood and which need more study. We conclude with a set of recommendations for future research.     

Air pollutant emissions from the development,production, and processing of Marcellus Shale natural gas

The Marcellus Shale is one of the largest natural gas reserves in the United States; it has recently been the focus of intense drilling and leasing activity. This paper describes an air emissions inventory for the development, production, and processing of natural gas in the Marcellus Shale region for 2009 and 2020. It includes estimates of the emissions of oxides of nitrogen (NO_x), volatile organic compounds (VOCs), and primary fine particulate matter (≤2.5 µm aerodynamic diameter; PM_2.5) from major activities such as drilling, hydraulic fracturing, compressor stations, and completion venting. The inventory is constructed using a process-level approach; a Monte Carlo analysis is used to explicitly account for the uncertainty. Emissions were estimated for 2009 and projected to 2020, accounting for the effects of existing and potential additional regulations. In 2020, Marcellus activities are predicted to contribute 6–18% (95% confidence interval) of the NO_x emissions in the Marcellus region, with an average contribution of 12% (129 tons/day). In 2020, the predicted contribution of Marcellus activities to the regional anthropogenic VOC emissions ranged between 7% and 28% (95% confidence interval), with an average contribution of 12% (100 tons/day). These estimates account for the implementation of recently promulgated regulations such as the Tier 4 off-road diesel engine regulation and the U.S. Environmental Protection Agency's (EPA) Oil and Gas Rule. These regulations significantly reduce the Marcellus VOC and NO_x emissions, but there are significant opportunities for further reduction in these emissions using existing technologies.

Implications: The Marcellus Shale is one of the largest natural gas reserves in United States. The development and production of this gas may emit substantial amounts of oxides of nitrogen and volatile organic compounds. These emissions may have special significance because Marcellus development is occurring close to areas that have been designated nonattainment for the ozone standard. Control technologies exist to substantially reduce these impacts. PM_2.5 emissions are predicted to be negligible in a regional context, but elemental carbon emissions from diesel powered equipment may be important.     

An exploratory study of air emissions associated with shale gas development and production in the Barnett Shale

Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a “fingerprint” of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8–2.0 ppm_v). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression.

Implications: Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.     

An Operational Assessment of the Application of the Relative Reduction Factors in the Demonstration of Attainment of the 8-Hr Ozone National Ambient Air Quality Standard

Abstract

The U.S. Environmental Protection Agency in 1997 revised the 1-hr ozone (O₃) National Ambient Air Quality Standard (NAAQS) to one based on an 8-hr average, resulting in potential nonattainment status for substantial portions of the eastern United States. The regulatory process provides for the development of a state implementation plan that includes a demonstration that the projected future O₃ concentrations will be at or below the NAAQS based on photochemical modeling and analytical techniques.

In this study, four photochemical modeling systems, based on two photochemical models, Community Model for Air Quality and the Comprehensive Air Quality Model with extensions, and two emissions processing models, Sparse Matrix Optimization Kernel for Emissions and Emissions Modeling System, were applied to the eastern United States, with emphasis on the northeastern Ozone Transport Region in terms of their response to oxides of nitrogen and volatile organic carbon-focused controls on the estimated design values. With the 8-hr O₃ NAAQS set as a bright-line test, it was found that a given area could be termed as being in or out of attainment of the NAAQS depending upon the modeling system. This suggests the need to provide an estimate of model-to-model uncertainty in the relative reduction factor (RRF) for a better understanding of the uncertainty in projecting the status of an area's attainment. Results indicate that the model-to-model differences considered in this study introduce an uncertainty of the future estimated design value of ～3–5 ppb.     

The impact of municipal solid waste management on greenhouse gas emissions in the United States

Technological advancements, environmental regulations, and emphasis on resource conservation and recovery have greatly reduced the environmental impacts of municipal solid waste (MSW) management, including emissions of greenhouse gases (GHGs). This study was conducted using a life-cycle methodology to track changes in GHG emissions during the past 25 years from the management of MSW in the United States. For the baseline year of 1974, MSW management consisted of limited recycling, combustion without energy recovery, and landfilling without gas collection or control. This was compared with data for 1980, 1990, and 1997, accounting for changes in MSW quantity, composition, management practices, and technology. Over time, the United States has moved toward increased recycling, composting, combustion (with energy recovery) and landfilling with gas recovery, control, and utilization. These changes were accounted for with historical data on MSW composition, quantities, management practices, and technological changes. Included in the analysis were the benefits of materials recycling and energy recovery to the extent that these displace virgin raw materials and fossil fuel electricity production, respectively. Carbon sinks associated with MSW management also were addressed. The results indicate that the MSW management actions taken by U.S. communities have significantly reduced potential GHG emissions despite an almost 2-fold increase in waste generation. GHG emissions from MSW management were estimated to be 36 million metric tons carbon equivalents (MMTCE) in 1974 and 8 MMTCE in 1997. If MSW were being managed today as it was in 1974, GHG emissions would be approximately 60 MMTCE.     

Exhaust Emissions From In-Use Alternative Fuel Vehicles

Abstract

This study examines exhaust emissions from 11 vehicles tested on compressed natural gas, liquefied petroleum gas, methanol, ethanol, and reformulated gasoline fuels (22 vehicle/ fuel combinations). The paper highlights ozone precursor and toxic emissions. Emission rates from some of the presumably well-maintained, low-mileage test vehicles were higher than expected, but fuel effects were consistent with findings of similar studies. Aggregate toxic and non-methane organic emission rates from the variable/flexible fuel vehicles were higher with alcohol fuels than with reformulated gasoline. Lower specific reactivities for emissions with the alcohol fuels offset this negative trait. Specific reactivities of the organic emissions with the alternative fuels were consistently lower than those with the gasoline blends. Compressed natural gas and liquefied petroleum gas fuels had the lowest values. Although specific reactivities were expected to vary from fuel-to-fuel, they also varied considerably from vehicle-to-vehicle.     

Evaluation of the Use of Diffusive Air Samplers for Determining Temporal and Spatial Variation of Volatile Organic Compounds in the Ambient Air of Urban Communities

Abstract

The Houston-Galveston metropolitan area has a relatively high density of point and mobile sources of air toxics, and determining and understanding the relationship between emissions and ambient air concentrations of air toxics is important for evaluating potential impacts on public health and formulating effective regulatory policies to control this impact, both in this region and elsewhere. However, conventional ambient air monitoring approaches are limited with regard to expense, siting limitations, and representative sampling necessary for adequate exposure assessment. The overall goal of this multiphase study is to evaluate the use of simple passive air samplers to determine temporal and spatial variability of the ambient air concentrations of selected volatile organic compounds (VOCs) in urban areas. Phase 1 of this study, reported here, was a field evaluation of 3M organic vapor monitors (OVMs) involving limited comparisons with commonly used active sampling methods, an assessment of sampler precision, a determination of optimal sampling duration, and an investigation of the utility of a simple modification of the commercial sampler. The results indicated that a sampling duration of 72 hr exhibited generally low bias relative to automated continuous gas chromatography measurements, good overall precision, and an acceptable number of measurements above detection limits. The modified sampler showed good correlation with the commercial sampler, with higher sampling rates, although lower than expected.     

Catalytic oxidation of organic compounds in incineration flue gas by a commercial palladium catalyst

The object of this study is to investigate the effect of different operation conditions on the catalytic oxidation of trace organic compounds [i.e., benzene, toluene, ethylbenzene, and xylene (BTEX); and polyaromatic hydrocarbons (PAHs)] in incineration flue gas. A commercial Pd-based honeycomb catalyst, which is applied to treat flue gas with low organic concentrations and high gas velocity, is employed in this study. The investigated parameters include (1) effect of different space velocities, (2) effect of heavy metals, (3) effect of acid gas, and (4) effect of water vapor and ash particles. In this work, an effective catalyst oxidation system is constructed and expected to purify the incineration flue gas. Catalyst oxidation is a potential purification system that will meet the stricter regulations on the emissions of incineration systems. Experimental results showed that the destruction efficiency of PAHs and BTEX in Pd catalyst was generally greater than 80%. Decreasing the space velocity increased the decomposition efficiency of organic compounds. When the feedstock contained the heavy metals Pb and Cr, the oxidation of organic compounds was not inhibited. But the presence of Cd significantly decreased the oxidation efficiency. The acid gases SO2 and HCl in the flue gas could have influenced the crystal structure of PdO and subsequently deactivated/poisoned the Pd catalyst. The effect of water vapor on the catalytic destruction of PAHs and BTEX was not obvious.     

Response of Fine Particulate Matter to Emission Changes of Oxides of Nitrogen and Anthropogenic Volatile Organic Compounds in the Eastern United States

Abstract

A three-dimensional chemical transport model (Particulate Matter Comprehensive Air Quality Model with Extensions [PMCAMx]) is used to investigate changes in fine particle (PM_2.5) concentrations in response to 50% emissions changes of oxides of nitrogen (NO_x) and anthropogenic volatile organic compounds (VOCs) during July 2001 and January 2002 in the eastern United States. The reduction of NO_x emissions by 50% during the summer results in lower average oxidant levels and lowers PM_2.5 (8% on average), mainly because of reductions of sulfate (9–11%), nitrate (45–58%), and ammonium (7–11%). The organic particulate matter (PM) slightly decreases in rural areas, whereas it increases in cities by a few percent when NO_x is reduced. Reduction of NO_x during winter causes an increase of the oxidant levels and a rather complicated response of the PM components, leading to small net changes. Sulfate increases (8–17%), nitrate decreases (18– 42%), organic PM slightly increases, and ammonium either increases or decreases a little. The reduction of VOC emissions during the summer causes on average a small increase of the oxidant levels and a marginal increase in PM_2.5. This small net change is due to increases in the inorganic components and decreases of the organic ones. Reduction of VOC emissions during winter results in a decrease of the oxidant levels and a 5–10% reduction of PM_2.5 because of reductions in nitrate (4–19%), ammonium (4–10%), organic PM (12–14%), and small reductions in sulfate. Although sulfur dioxide (SO₂) reduction is the single most effective approach for sulfate control, the coupled decrease of SO₂ and NO_x emissions in both seasons is more effective in reducing total PM_2.5 mass than the SO₂ reduction alone.     

Measurements show that marginal wells are a disproportionate source of methane relative to production

ABSTRACT

Oil and natural gas wells are a prominent source of the greenhouse gas methane (CH₄), but most measurements are from newer, high producing wells. There are nearly 700,000 marginal “stripper” wells in the US, which produce less than 15 barrels of oil equivalent (BOE) d^?1. We made direct measurements of CH₄ and volatile organic carbon (VOC) emissions from marginal oil and gas wells in the Appalachian Basin of southeastern Ohio, all producing < 1 BOE d^?1. Methane and VOC emissions followed a skewed distribution, with many wells having zero or low emissions and a few wells responsible for the majority of emissions. The average CH₄ emission rate from marginal wells was 128 g h^?1 (median: 18 g h^?1; range: 0– 907 g h^?1). Follow-up measurements at five wells indicated high emissions were not episodic. Some wells were emitting all or more of the reported gas produced at each well, or venting gas from wells with no reported gas production. Measurements were made from wellheads only, not tanks, so our estimates may be conservative. Stochastic processes such as maintenance may be the main driver of emissions. Marginal wells are a disproportionate source of CH₄ and VOCs relative to oil and gas production. We estimate that oil and gas wells in this lowest production category emit approximately 11% of total annual CH₄ from oil and gas production in the EPA greenhouse gas inventory, although they produce about 0.2% of oil and 0.4% of gas in the US per year.

Implications: Low producing marginal wells are the most abundant type of oil and gas well in the United States, and a surprising number of them are venting all or more of their reported produced gas to the atmosphere. This makes marginal wells a disproportionate greenhouse gas emissions source compared to their energy return, and a good target for environmental mitigation.     

Characterization of Sonic Devices Used for Cleaning Fabric Filters

ABSTRACT

Ozone reactivity scales play an important role in selecting which chemical compounds are used in products ranging from gasoline to pesticides to hairspray in California, across the United States and around the world. The California Statewide Air Pollution Research Center (SAPRC) box model that calculates ozone reactivity uses a representative urban atmosphere to predict how much additional ozone forms for each kilogram of compound emission. This representative urban atmosphere has remained constant since 1988, even though more than 25 years of emissions controls have greatly reduced ambient ozone concentrations across the United States during this time period. Here we explore the effects of updating the representative urban atmosphere used for ozone reactivity calculations from 1988 to 2010 conditions by updating the meteorology, emission rates, concentration of initial conditions, concentration of background species, and composition of volatile organic compound (VOC) profiles. Box model scenarios are explored for 39 cities across the United States to calculate the Maximum Incremental Reactivity (MIR) scale for 1,233 individual compounds and compound-mixtures. Median MIR values across the cities decreased by approximately 20.3% when model conditions were updated. The decrease is primarily due to changes in atmospheric composition ultimately attributable to emissions control programs between 1998 and 2010. Further effects were caused by changes in meteorological variables stemming from shifting seasons for peak ozone events (summer versus early fall). Lumped model species with the highest MIR values in 1988 experienced the greatest decrease in MIR values when conditions were updated to 2010. Despite the reduction in the absolute reactivity in the updated 2010 atmosphere, the relative ranking of the VOCs according to their reactivity did not change strongly compared to the original 1988 atmosphere. These findings indicate that past decisions about ozone control programs remain valid today, and the ozone reactivity scale continues to provide relevant guidance for future policy decisions even as new products are developed.

Implications: Updating the representative urban atmosphere used for the Maximum Incremental Reactivity (MIR) scale from 1988 to 2010 conditions caused the reactivity of 1223 individual compounds and combined mixtures to decrease by an average of 20.3% but the relative ranking of the VOCs was not strongly affected. This means that previous guidance about preferred chemical formulations to reduce ozone formation in cities across the United States remain valid today, and the MIR scale continues to provide relevant guidance for future policy decisions even as new products are developed.     

Issues and Trends in Electrostatic Precipitation Technology for U.S. Utilities

The pace and direction of electrostatic precipitator (ESP) technology evolution in the United States will be governed by two key forces. The first is new clean air legislation passed by the U.S. Congress and signed by President Bush on November 15,1990. This law requires electric utilities to further reduce SO₂ and NO_x emissions, which may impact particulate controls. In addition, very fine (< 10 micron) participates and potentially toxic trace emissions from utility power plants may be regulated. The second major factor is the expected upsurge in new plant construction beginning in the late 1990s. Together, these forces should define the performance requirements and market for new ESPs.

This paper identifies and briefly describes technologies that the Electric Power Research Institute (EPRI) is developing to help U.S. utilities meet these challenges cost-effectively. Among the technologies addressed are: advanced digital voltage controls, flue gas conditioning, intermittent energization, temperature-controlledprecharging (i.e., two-stage ESP), wide plate spacing, positive energization of corona electrodes for hot-side ESPs, and integration of conventional ESPs with pulse-jet baghouses.     

Indoor Emissions from Conversion Varnishes

ABSTRACT

Conversion varnishes are two-component, acid-catalyzed varnishes that are commonly used to finish cabinets. They are valued for their water and stain resistance, as well as their appearance. They have been found, however, to contribute to indoor emissions of organic compounds. For this project, three commercially available conversion varnish systems were selected. A U.S. Environmental Protection Agency (EPA) Method 24 analysis was performed to determine total volatile content, and a sodium sulfite titration method was used to determine uncombined (free) formaldehyde content of the varnish components. The resin component was also analyzed by gas chromatography/mass spectroscopy (GC/MS) (EPA Method 311 with an MS detector) to identify individual organic compounds. Dynamic small chamber tests were then performed to identify and quantify emissions following application to coupons of typical kitchen cabinet wood substrates, during both curing and aging. Because conversion varnishes cure by chemical reaction, the compounds emitted during curing and aging are not necessarily the same as those in the formulation. Results of small chamber tests showed that the amount of formaldehyde emitted from these coatings was 2.3–8.1 times the amount of free formaldehyde applied in the coatings. A long-term test showed a formaldehyde emission rate of 0.17 mg/m²/hr after 115 days.     

Remote sensing-based estimates of annual and seasonal emissions from crop residue burning in the contiguous United States

Crop residue burning is an extensive agricultural practice in the contiguous United States (CONUS). This analysis presents the results of a remote sensing-based study of crop residue burning emissions in the CONUS for the time period 2003-2007 for the atmospheric species of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2, sulfur dioxide (SO2), PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter), and PM10 (PM < or = 10 microm in aerodynamic diameter). Cropland burned area and associated crop types were derived from Moderate Resolution Imaging Spectroradiometer (MODIS) products. Emission factors, fuel load, and combustion completeness estimates were derived from the scientific literature, governmental reports, and expert knowledge. Emissions were calculated using the bottom-up approach in which emissions are the product of burned area, fuel load, and combustion completeness for each specific crop type. On average, annual crop residue burning in the CONUS emitted 6.1 Tg of CO2, 8.9 Gg of CH4, 232.4 Gg of CO, 10.6 Gg of NO2, 4.4 Gg of SO2, 20.9 Gg of PM2.5, and 28.5 Gg of PM10. These emissions remained fairly consistent, with an average interannual variability of crop residue burning emissions of +/- 10%. The states with the highest emissions were Arkansas, California, Florida, Idaho, Texas, and Washington. Most emissions were clustered in the southeastern United States, the Great Plains, and the Pacific Northwest. Air quality and carbon emissions were concentrated in the spring, summer, and fall, with an exception because of winter harvesting of sugarcane in Florida, Louisiana, and Texas. Sugarcane, wheat, and rice residues accounted for approximately 70% of all crop residue burning and associated emissions. Estimates of CO and CH4 from agricultural waste burning by the U.S. Environmental Protection Agency were 73 and 78% higher than the CO and CH4 emission estimates from this analysis, respectively. This analysis also showed that crop residue burning emissions are a minor source of CH4 emissions (< 1%) compared with the CH4 emissions from other agricultural sources, specifically enteric fermentation, manure management, and rice cultivation.