Emission strength validation using four-dimensional data assimilation: application to primary aerosol and precursors to ozone and secondary aerosol.

Three-dimensional air quality models (AQMs) represent the most powerful tool to follow the dynamics of air pollutants at urban and regional scales. Current AQMs can account for the complex interactions between gas-phase chemistry, aerosol growth, cloud and scavenging processes, and transport. However, errors in model applications still exist due in part to limitations in the models themselves and in part to uncertainties in model inputs. Four-dimensional data assimilation (FDDA) can be used as a top-down tool to validate several of the model inputs, including emissions inventories, based on ambient measurements. Previously, this FDDA technique was used to estimate adjustments in the strength and composition of emissions of gas-phase primary species and O3 precursors. In this paper, we present an extension to the FDDA technique to incorporate the analysis of particulate matter (PM) and its precursors. The FDDA approach consists of an iterative optimization procedure in which an AQM is coupled to an inverse model, and adjusting the emissions minimizes the difference between ambient measurements and model-derived concentrations. Here, the FDDA technique was applied to two episodes, with the modeling domain covering the eastern United States, to derive emission adjustments of domainwide sources of NO., volatile organic compounds (VOCs), CO, SO2, NH3, and fine organic aerosol emissions. Ambient measurements used include gas-phase inorganic and organic species and speciated fine PM. Results for the base-case inventories used here indicate that emissions of SO2 and CO appear to be estimated reasonably well (requiring minor revisions), while emissions of NOx, VOC, NH3, and organic PM with aerodynamic diameter less than 2.5 microm (PM2.5) require more significant revision.     

Directions for Combustion Engine Aerosol Measurement in the 21st Century

Abstract

The Coordinating Research Council convened two Real-Time PM Measurement Workshops in December 2008 and March 2009 to take an intensive look at the current status and future directions of combustion aerosol measurement. The purpose was to examine the implications of parallel rapid developments over the past decade in ambient aerosol science, engine aftertreatment technology, and aerosol measurement methodology, which provide bene?ts and challenges to the stakeholders in air quality management. The workshops were organized into sessions targeting key issues in ambient and source combustion particulate matter (PM). These include (1) metrics to characterize and quantify PM, (2) the need to reconcile ambient and source measurements, (3) the role of atmospheric transformations on modeling emissions and exposures, (4) the impact of sampling conditions on PM measurement, and (5) the potential bene?ts of novel PM instrumentation. This paper distills the material presented by subject experts and the insights derived from the in-depth discussions that formed the core of each session. The paper’s objectives are to identify areas of consensus that allow wider practical application of the past decade’s advances in combustion aerosol measurement to improve emissions and air quality modeling, develop emissions reduction strategies, and to recommend directions for progress on issues in which uncertainties remain.     

Locating the Offender

Abstract

The Coordinating Research Council held its thirteenth Vehicle Emissions Workshop in April 2003, when results of the most recent on-road vehicle emissions research were presented. Ongoing work from researchers who are engaged in improving understanding of the contribution of mobile sources to ambient air quality and emission inventories is summarized here. Participants in the workshop discussed efforts to improve mobile source emission models, the role of on-board diagnostic systems in inspection and maintenance programs, light- and heavy-duty vehicle emissions measurements, on- and off-road emissions measurements, effects of fuels and lubricating oils on emissions, as well as topics for future research.     

The sensitivity of modeled ozone to the temporal distribution of point, area, and mobile source emissions in the eastern United States

Ozone remains one of the most recalcitrant air pollution problems in the US. Hourly emissions fields used in air quality models (AQMs) generally show less temporal variability than corresponding measurements from continuous emissions monitors (CEM) and field campaigns would imply. If emissions control scenarios to reduce emissions at peak ozone forming hours are to be assessed with AQMs, the effect of emissions' daily variability on modeled ozone must be understood. We analyzed the effects of altering all anthropogenic emissions' temporal distributions by source group on 2002 summer-long simulations of ozone using the Community Multiscale Air Quality Model (CMAQ) v4.5 and the Carbon Bond IV (CBIV) chemical mechanism with 12 km resolution. We find that when mobile source emissions were made constant over the course of a day, 8-h maximum ozone predictions changed by ±7 parts per billion by volume (ppbv) in many urban areas on days when ozone concentrations greater than 80 ppbv were simulated in the base case. Increasing the temporal variation of point sources resulted in ozone changes of +6 and −6 ppbv, but only for small areas near sources. Changing the daily cycle of mobile source emissions produces substantial changes in simulated ozone, especially in urban areas at night; results suggest that shifting the emissions of NO_x from day to night, for example in electric powered vehicles recharged at night, could have beneficial impacts on air quality.     

Emission and Fate Assessment of Methyl Tertiary Butyl Ether in the Boston Area Airshed Using a Simple Multimedia Box Model: Comparison with Urban Air Measurements

Abstract

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 [H9262]g/m³ MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 μg/m³ and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (.OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

Spatial Modeling for Air Pollution Monitoring Network Design: Example of Residential Woodsmoke

Abstract

The purpose of this paper is to demonstrate how to develop an air pollution monitoring network to characterize small-area spatial contrasts in ambient air pollution concentrations. Using residential woodburning emissions as our case study, this paper reports on the first three stages of a four-stage protocol to measure, estimate, and validate ambient residential woodsmoke emissions in Vancouver, British Columbia. The first step is to develop an initial winter nighttime woodsmoke emissions surface using inverse-distance weighting of emissions information from consumer woodburning surveys and property assessment data. Second, fireplace density and a compound topo-graphic index based on hydrological flow regimes are used to enhance the emissions surface. Third, the spatial variation of the surface is used in a location-allocation algorithm to design a network of samplers for the woodsmoke tracer compound levoglucosan and fine particulate matter. Measurements at these network sites are then used in the fourth stage of the protocol (not presented here): a mobile sampling campaign aimed at developing a high-resolution surface of woodsmoke concentrations for exposure assignment in health effects studies. Overall the results show that relatively simple data inputs and spatial analysis can be effective in capturing the spatial variability of ambient air pollution emissions and concentrations.     

Uncertainty Analysis of Ozone Formation and Response to Emission Controls Using Higher-Order Sensitivities

Abstract

Understanding ozone response to its precursor emissions is crucial for effective air quality management practices. This nonlinear response is usually simulated using chemical transport models, and the modeling results are affected by uncertainties in emissions inputs. In this study, a high ozone episode in the southeastern United States is simulated using the Community Multiscale Air Quality (CMAQ) model. Uncertainties in ozone formation and response to emissions controls due to uncertainties in emission rates are quantified using the Monte Carlo method. Instead of propagating emissions uncertainties through the original CMAQ, a reduced form of CMAQ is formulated using directly calculated first- and second-order sensitivities that capture the nonlinear ozone concentration-emission responses. This modification greatly reduces the associated computational cost. Quantified uncertainties in modeled ozone concentrations and responses to various emissions controls are much less than the uncertainties in emissions inputs. Average uncertainties in modeled ozone concentrations for the Atlanta area are less than 10% (as measured by the inferred coefficient of variance [ICOV]) even when emissions uncertainties are assumed to vary between a factor of 1.5 and 2. Uncertainties in the ozone responses generally decrease with increased emission controls. Average uncertainties (ICOV) in emission-normalized ozone responses range from 4 to 22%, with the smaller being associated with controlling of the relatively certain point nitrogen oxide (NO_x) emissions and the larger resulting from controlling of the less certain mobile NO_x emissions. These small uncertainties provide confidence in the model applications, such as in performance evaluation, attainment demonstration, and control strategy development.     

Objectives and Design of Central California's 1995 Integrated Monitoring Study of the California Regional PM10/PM2.5 Air Quality Study

ABSTRACT

The 1995 Integrated Monitoring Study (IMS95) is part of the Phase 1 planning efforts for the California Regional PM_10/PM_2.5 Air Quality Study. Thus, the overall objectives of IMS95 are to (1) fill information gaps needed for planning an effective field program later this decade; (2) develop an improved conceptual model for pollution buildup (PM10, PM2.5, and aerosol precursors) in the San Joaquin Valley; (3) develop a uniform air quality, meteorological, and emissions database that can be used to perform initial evaluations of aerosol and fog air quality models; and (4) provide early products that can be used to help with the development of State Implementation Plans for PM_10. Consideration of the new particulate matter standards were also included in the planning and design of IMS95, although they were proposed standards when IMS95 was in the planning process.     

Development of Instrumentation for Continuous On-line Monitoring of Non-Methane Organic Carbon in Air Emissions

ABSTRACT

Non-methane organic carbon (NMOC) is a measure of total organic carbon in an air emission, excluding that from methane. Thus, it measures the total amount of carbon, irrespective of the structure and functional groups in the molecule. The U.S. Environmental Protection Agency (EPA) Method 25 is used for quantification of NMOC in emission sources and in ambient air. This method involves laboratory analysis of collected air samples and cannot be used for real-time measurements. It is prone to interferences from CO₂, CH₄, and CO, as well as moisture. In this paper, a novel method for continuous, on-line monitoring of NMOC in air emissions and ambient air is presented. Detection limits are at ppb levels, and interference of permanent gases have been eliminated.     

Development of a PM2 5 Emissions Inventory for the South Coast Air Basin

ABSTRACT

With the promulgation of a national PM_2.5 ambient air quality standard, it is important that PM_2.5 emissions inventories be developed as a tool for understanding the magnitude of potential PM2.5 violations. Current PM₁₀ inventories include only emissions of primary particulate matter (1 ^ï PM), whereas, based on ambient measurements, both PM₁₀ and PM2.5 emissions inventories will need to include sources of both 1^ï PM and secondary particulate matter (2^ï PM). Furthermore, the U. S. Environmental Protection Agency’s (EPA) current edition of AP-42 includes size distribution data for 1o PM that overestimate the PM_2.5 fraction of fugitive dust sources by at least a factor of 2 based on recent studies.

This paper presents a PM_2.5 emissions inventory developed for the South Coast Air Basin (SCAB) that for the first time includes both 1^ï PM and 2^ï PM. The former is calculated by multiplying PM₁₀ emissions estimates by the PM_2.5/PM₁₀ ratios for different sources. The latter is calculated from estimated emission rates of gas-phase aerosol precursor and gas to aerosol conversion rates consistent with the measured chemical composition of ambient PM_2.5 concentrations observed in the SCAB. The major finding of this PM_2.5 emissions inventory is that the ^2ï aerosol component is more than twice the ^1ï aerosol component, which may result in widely different control strategies being required for fine PM and coarse PM.     

Chemical Characterization of Emissions from Vegetable Oil Processing and Their Contribution to Aerosol Mass Using the Organic Molecular Markers Approach

ABSTRACT

The organic fraction of aerosol emitted from a vegetable oil processing plant was studied to investigate the contribution of emissions to ambient particles in the surrounding area. Solvent-soluble particulate organic compounds emitted from the plant accounted for 10% of total suspended particles. This percentage was lower in the receptor sites (less than 6% of total aerosol mass). Nonpolar, moderate polar, polar, and acidic compounds were detected in both emitted and ambient aerosol samples. The processing and combustion of olive pits yielded a source with strong biogenic characteristics, such as the high values of the carbon preference index (CPI) for all compound classes. Polycyclic aromatic hydrocarbons (PAHs) detected in emissions were associated with both olive pits and diesel combustion. The chromatographic profile of dimethyl-phenanthrenes (DMPs) was characteristic of olive pit combustion. Organic aerosols collected in two receptor sites provided a different pattern.

The significant contribution of vehicular emissions was identified by CPI values (~1) of n-alkanes and the presence of the unresolved complex mixture (UCM). In addition, PAH concentration diagnostic ratios indicated that emissions from catalyst and noncatalyst automobiles and heavy trucks were significant. The strong even-to-odd predominance of n-alkanols, n-alkanoic acids, and their salts indicated the contribution of a source with biogenic characteristics. However, the profile of DMPs at receptor sites was similar to that observed for diesel particulates. These differences indicated that the contribution of vegetable oil processing emissions to the atmosphere was negligible.     

Odor Control In Los Angeles County

Abstract

Concentrations of 38 gas-phase organic air toxics were measured over a 2-yr period at four different sites in and around Pittsburgh, PA, to investigate spatial variations in health risks from chronic exposure. The sites were chosen to represent different exposure regimes: a downtown site with substantial mobile source emissions; two residential sites adjacent to one of the most heavily industrialized zones in Pittsburgh; and a regional background site. Lifetime cancer risks and non-cancer hazard quotients were estimated using a traditional and interactive risk models. Although study average concentrations of specific air toxics varied by as a much as a factor of 26 between the sites, the additive cancer risks of the gas-phase organic air toxics varied by less than a factor of 2, ranging from 6.1 × 10^-5 to 9.5 × 10^-5. The modest variation in risks reflects the fact that two regionally distributed toxics, formalde-hyde and carbon tetrachloride (CCl₄), contributed more than half of the cancer risk at all four sites. Benzene contributed substantial cancer risks at all sites, whereas trichloroethene and 1,4-dichlorobenzene only contributed substantial cancer risks at the downtown site. Only acrolein posed a non-cancer risk. Diesel particulate matter is estimated to pose a much greater cancer risk in Pittsburgh than other classes of air toxics including gas-phase organic, metals, polycyclic aromatic hydrocarbons, and coke oven emissions. Health risks of air toxics in Pittsburgh are comparable with those in other urban areas in the United States.     

Sensitivity of Source Apportionment of Urban Particulate Matter to Uncertainty in Motor Vehicle Emissions Profiles

Abstract

A sensitivity analysis was conducted to characterize sources of uncertainty in results of a molecular marker source apportionment model of ambient particulate matter using mobile source emissions profiles obtained as part of the Gasoline/Diesel PM Split Study. A chemical mass balance (CMB) model was used to determine source contributions to samples of fine particulate matter (PM_2.5) collected over 3 weeks at two sites in the Los Angeles area in July 2001. The ambient samples were composited for organic compound analysis by the day of the week to investigate weekly trends in source contributions. The sensitivity analysis specifically examined the impact of the uncertainty in mobile source emissions profiles on the CMB model results. The key parameter impacting model sensitivity was the source profile for gasoline smoker vehicles. High-emitting gasoline smoker vehicles with visible plumes were seen to be a significant source of PM in the area, but use of different measured profiles for smoker vehicles in the model gave very different results for apportionment of gasoline, diesel, and smoker vehicle tailpipe emissions. In addition, the contributions of gasoline and diesel emissions to total ambient PM varied as a function of the site and the day of the week.     

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.     

Characterization of air manganese exposure estimates for residents in two Ohio towns

This study was conducted to derive receptor-specific outdoor exposure concentrations of total suspended particulate (TSP) and respirable (d_ae ≤ 10 µm) air manganese (air-Mn) for East Liverpool and Marietta (Ohio) in the absence of facility emissions data, but where long-term air measurements were available. Our “site-surface area emissions method” used U.S. Environmental Protection Agency’s (EPA) AERMOD (AMS/EPA Regulatory Model) dispersion model and air measurement data to estimate concentrations for residential receptor sites in the two communities. Modeled concentrations were used to create ratios between receptor points and calibrated using measured data from local air monitoring stations. Estimated outdoor air-Mn concentrations were derived for individual study subjects in both towns. The mean estimated long-term air-Mn exposure levels for total suspended particulate were 0.35 μg/m³ (geometric mean [GM]) and 0.88 μg/m³ (arithmetic mean [AM]) in East Liverpool (range: 0.014–6.32 μg/m³) and 0.17 μg/m³ (GM) and 0.21 μg/m³ (AM) in Marietta (range: 0.03–1.61 μg/m³). Modeled results compared well with averaged ambient air measurements from local air monitoring stations. Exposure to respirable Mn particulate matter (PM₁₀; PM <10 μm) was higher in Marietta residents.

Implications: Few available studies evaluate long-term health outcomes from inhalational manganese (Mn) exposure in residential populations, due in part to challenges in measuring individual exposures. Local long-term air measurements provide the means to calibrate models used in estimating long-term exposures. Furthermore, this combination of modeling and ambient air sampling can be used to derive receptor-specific exposure estimates even in the absence of source emissions data for use in human health outcome studies.     

An Empirical Model to Predict Styrene Emissions from Fiber-Reinforced Plastics Fabrication Processes

ABSTRACT

Styrene is a designated hazardous air pollutant, per the 1990 Clean Air Act Amendments. It is also a tropospheric ozone precursor. Fiber-reinforced plastics (FRP) fabrication is the primary source of anthropogenic styrene emissions in the United States. This paper describes an empirical model designed to predict styrene emission factors for selected FRP fabrication processes. The model highlights 10 relevant parameters impacting styrene emission factors for FRP processes, and helps identify future areas of FRP pollution prevention (P2) research. In most cases, the number of these parameters with greatest impact on styrene emission factors can be limited to four or five. Seven different emission studies were evaluated and used as model inputs.     

Human Breath Emissions of VOCs

ABSTRACT

The medical community has long recognized that humans exhale volatile organic compounds (VOCs). Several studies have quantified emissions of VOCs from human breath, with values ranging widely due to variation between and within individuals. The authors have measured human breath concentrations of isoprene and pentane. The major VOCs in the breath of healthy individuals are isoprene (12580 ppb), acetone (1.2-1,880 ppb), ethanol (13-1,000 ppb), methanol (160-2,000 ppb) and other alcohols. In this study, we give a brief summary of VOC measurements in human breath and discuss their implications for indoor concentrations of these compounds, their contributions to regional and global emissions budgets, and potential ambient air sampling artifacts. Though human breath emissions are a negligible source of VOCs on regional and global scales (less than 4% and 0.3%, respectively), simple box model calculations indicate that they may become an important (and sometimes major) indoor source of VOCs under crowded conditions. Human breath emissions are generally not taken into account in indoor air studies, and results from this study suggest that they should be.     

The Use of Ambient Measurements To Identify which Precursor Species Limit Aerosol Nitrate Formation

ABSTRACT

A thermodynamic equilibrium model was used to investigate the response of aerosol NO₃ to changes in concentrations of HNO₃, NH₃, and H₂SO₄. Over a range of temperatures and relative humidities (RHs), two parameters provided sufficient information for indicating the qualitative response of aerosol NO₃. The first was the excess of aerosol NH₄ ⁺ plus gas-phase NH₃ over the sum of HNO₃, particulate NO₃, and particulate SO₄ ^2- concentrations. The second was the ratio of particulate to total NO₃ concentrations. Computation of these quantities from ambient measurements provides a means to rapidly analyze large numbers of samples and identify cases in which inorganic aerosol NO₃ formation is limited by the availability of NH₃. Example calculations are presented using data from three field studies. The predictions of the indicator variables and the equilibrium model are compared.     

Contribution of Liquefied Petroleum Gas to Air Pollution in the Metropolitan Area of Mexico City

ABSTRACT

An estimation of hydrocarbon emissions caused by the consumption of liquefied petroleum gas (LPG) in the Metropolitan Area of Mexico City (MAMC) is presented. On the basis of experimental measurements at all points of handling, during the distribution process, and during the consumption of LPG in industrial devices and domestic appliances, an estimated 76,414 tons/year are released to the air. The most important contribution is found during the domestic consumption of LPG (70%); this makes the control initiatives available to the consumer. By developing a control program of LPG losses, a 77% reduction in emission is expected in a 5-yr period.

The calculated amounts of LPG emissions when correlated with the consumption of LPG, combined with information from air samples from the MAMC, do not point to LPG emissions as the most important factor contributing to tropospheric ozone in the air in Mexico City.     

Analysis and Simulation of Wintertime Light Scattering by the Urban Aerosol in Dallas-Fort Worth

ABSTRACT

Wintertime atmospheric light scattering in Dallas, TX, was estimated through the use of aerosol models. Input data for the aerosol models were provided by measurements of aerosol chemistry, physical particle size distributions, and distributions of particulate sulfur by particle size, and by predictions by an atmospheric simulation model. Light scattering measurements provided a basis for testing the aerosol models. The SCAPE thermodynamic equilibrium model was used to estimate the amount of liquid water associated with particles and the ELSIE Mie scattering model was applied to estimate the resulting light scattering. The calculations were based on aerosol properties measured in Dallas during December 1994 and February 1995, and changes in scattering due to hypothetical changes in the aerosol were predicted. The predicted light scattering was compared to scattering measured by an Optec nephelom-eter; agreement was within 20% in every case.