Concentrations of mobile source air pollutants in urban microenvironments

Human exposures to criteria and hazardous air pollutants (HAPs) in urban areas vary greatly due to temporal-spatial variations in emissions, changing meteorology, varying proximity to sources, as well as due to building, vehicle, and other environmental characteristics that influence the amounts of ambient pollutants that penetrate or infiltrate into these microenvironments. Consequently, the exposure estimates derived from central-site ambient measurements are uncertain and tend to underestimate actual exposures. The Exposure Classification Project (ECP) was conducted to measure pollutant concentrations for common urban microenvironments (MEs) for use in evaluating the results of regulatory human exposure models. Nearly 500 sets of measurements were made in three Los Angeles County communities during fall 2008, winter 2009, and summer 2009. MEs included in-vehicle, near-road, outdoor, and indoor locations accessible to the general public. Contemporaneous 1- to 15-min average personal breathing zone concentrations of carbon monoxide (CO), carbon dioxide (CO₂), volatile organic compounds (VOCs), nitric oxide (NO), nitrogen oxides (NO_x), particulate matter (<2.5 μm diameter; PM_2.5) mass, ultrafine particle (UFP; <100 nm diameter) number, black carbon (BC), speciated HAPs (e.g., benzene, toluene, ethylbenzene, xylenes [BTEX], 1,3-butadiene), and ozone (O₃) were measured continuously. In-vehicle and inside/outside measurements were made in various passenger vehicle types and in public buildings to estimate penetration or infiltration factors. A large fraction of the observed pollutant concentrations for on-road MEs, especially near diesel trucks, was unrelated to ambient measurements at nearby monitors. Comparisons of ME concentrations estimated using the median ME/ambient ratio versus regression slopes and intercepts indicate that the regression approach may be more accurate for on-road MEs. Ranges in the ME/ambient ratios among ME categories were generally greater than differences among the three communities for the same ME category, suggesting that the ME proximity factors may be more broadly applicable to urban MEs.

Implications:Estimates of population exposure to air pollutants extrapolated from ambient measurements at ambient fixed site monitors or exposure surrogates are prone to uncertainty. This study measured concentrations of mobile source air toxics (MSAT) and related criteria pollutants within in-vehicle, outdoor near-road, and indoor urban MEs to provide multipollutant ME measurements that can be used to calibrate regulatory exposure models.     

Optimization-Based Atmospheric Plume Source Identification

This work applies optimization and an Eulerian inversion approach presented by Bagtzoglou and Baun in 2005 in order to reconstruct contaminant plume time histories and to identify the likely source of atmospheric contamination using data from a real test site for the first time. Present-day distribution of an atmospheric contaminant plume as well as data points reflecting the plume history allow the reconstruction and provide the plume velocity, distribution, and probable source. The method was tested to a hypothetical case and with data from the Forest Atmosphere Transfer and Storage (FACTS) experiment in the Duke experimental forest site. In the scenarios presented herein, as well as in numerous cases tested for verification purposes, the model conserved mass, successfully located the peak of the plume, and managed to capture the motion of the plume well but underestimated the contaminant peak.     

Dissolved phosphorus transport from soil to surface water in catchments with different land use

Diffuse phosphorus (P) export from agricultural land to surface waters is a significant environmental problem. It is critical to determine the natural background P losses from diffuse sources, but their identification and quantification is difficult. In this study, three headwater catchments with differing land use (arable, pasture and forest) were monitored for 3 years to quantify exports of dissolved (<0.45 µm) reactive P and total dissolved P. Mean total P exports from the arable catchment ranged between 0.08 and 0.28 kg ha^?1 year^?1. Compared with the reference condition (forest), arable land and pasture exported up to 11-fold more dissolved P. The contribution of dissolved (<0.45 µm) unreactive P was low to negligible in every catchment. Agricultural practices can exert large pressures on surface waters that are controlled by hydrological factors. Adapting policy to cope with these factors is needed for lowering these pressures in the future.     

Hydrocarbon Measurements During the 1992 Southern Oxidants Study Atlanta Intensive: Protocol and Quality Assurance

Abstract

A major component of the Southern Oxidants Study (SOS) 1992 Atlanta Intensive was the measurement of atmospheric nonmethane hydrocarbons. Ambient air samples were collected and analyzed by a network of strategically located automated gas chromatography (GC) systems (field systems). In addition, an extensive canister sampling network was deployed. Combined, more than 3000 chromatograms were recorded. The SOS science team targeted for quantitative analysis 56 compounds which may be substantial contributors to ozone formation or used as air mass tracers. A quality assurance program was instituted to ensure that good measurements were being made throughout the network for each target compound. Common, high-quality standards were used throughout the network. The performance of individual field systems was evaluated during the intensive through the analysis of challenge mixtures. This methodology helped to identify and correct analytical problems as they arose.     

Moving Bed Adsorption System for Control of VOCs from an Aircraft Painting Facility

An activated carbon moving bed system (10 to 100 acf m air flow) was tested for controlling VOC emissions from a commercial aircraft painting facility. The cross-flow moving adsorbent bed showed a VOC collection efficiency in the 77.1 to 99.6 percent range over a superficial gas velocity range of 27 to 185 ft/min (0.14-0.94 m/sec). The collection efficiencies were neither affected by a change in carbon flow rates from 5 to 8 Ib/hr (2.3 to 3.6 kg/hr) nor by a change in the gas superficial velocity from 27 to 185 ft/min. The VOC concentration in the emission stream from the painting hangar was found to vary by at least a factor of 20 (from 0.18 to 15 ppm) both over the five month period (during which the 15 system tests of about three hours each were conducted) and within a single eight hour work shift.     

The Southeastern Aerosol Research and Characterization Study: Part 1—Overview

Abstract

This paper presents an overview of a major, long-term program for tropospheric gas and aerosol research in the southeastern United States. Building on three existing ozone (O₃)-focused research sites begun in mid-1992, the Southeastern Aerosol Research and Characterization Study (SEARCH) was initiated in mid-1998 as a 7-year observation and research program with a broader focus including aerosols and an expanded geographical coverage in the Southeast. The monitoring network comprises four urban-rural (or urban-suburban) site pairs at locations along the coast of the Gulf of Mexico and inland, including two moderately sized and two major urban areas (Pensacola, FL; Gulfport, MS; Atlanta, GA; and Birmingham, AL). The sites are equipped with an extensive suite of instruments for measuring particulate matter (PM), gases relevant to secondary O₃ and the production of secondary aerosol particles, and surface meteorology. The measurements taken to date have added substantially to the knowledge about the temporal behavior and geographic variability of tropospheric aerosols in the Southeast. Details are presented in four papers to follow.     

An Assessment of the Emissions Inventory Processing Systems EMS-2001 and SMOKE in Grid-Based Air Quality Models

Abstract

In the United States, emission processing models such as Emissions Modeling System-2001 (EMS-2001), Emissions Preprocessor System-Version 2.5 (EPS2.5), and the Sparse Matrix Operator Kernel Emissions (SMOKE) model are currently being used to generate gridded, hourly, speciated emission inputs for urban and regional-scale photochemical models from aggregated pollutant inventories. In this study, two models, EMS-2001 and SMOKE, were applied with their default internal data sets to process a common inventory database for a high ozone (O₃) episode over the eastern United States using the Carbon Bond IV (CB4) chemical speciation mechanism. A comparison of the emissions processed by these systems shows differences in all three of the major processing steps performed by the two models (i.e., in temporal allocation, spatial allocation, and chemical speciation). Results from a simulation with a photochemical model using these two sets of emissions indicate differences on the order of ±20 ppb in the predicted 1-hr daily maximum O₃ concentrations. It is therefore critical to develop and implement more common and synchronized temporal, spatial, and speciation cross-reference systems such that the processes within each emissions model converge toward reasonably similar results. This would also help to increase confidence in the validity of photochemical grid model results by reducing one aspect of modeling uncertainty.     

IAPCS: A Computer Model that Evaluates Pollution Control Systems for Utility Boilers

The IAPCS model, developed by U.S. EPA’s Air and Energy Engineering Research Laboratory and made available to the public through the National Technical Information Service, can be used by utility companies, architectural and engineering companies, and regulatory agencies at all levels of government to evaluate commercially available technologies for control of SO₂, NO_x, and particulate matter emissions from coal-fired utility boilers with respect to performance and cost. The model is considered to be a useful tool to compare alternative control strategies to be used by utilities to comply with the requirements of the CAA, and to evaluate the sensitivity of control costs with respect to many of the significant variables affecting costs.

To illustrate the use of the model for site-specific studies, the authors used the model to estimate control costs for SO₂ and NO_x control at Detroit Edison’s Monroe plant and two hypothetical plants under consideration and at three plants operated by New York State Electric and Gas Corporation. The economic and technical assumptions used to drive the model were those proposed by the utilities if cited, and if not cited, the model default values were used. The economic format and methodologies for costs cited in the Electric Power Research Institute’s Technical Assessment Guide are used in the IAPCS model. Depending on the specific conditions and assumptions for the cases evaluated, SO₂ control costs ranged from $417 to $3,159 per ton of SO₂ removed, and NO_x control costs ranged from $461 to $3,537 per ton of NO_x removed or reduced.     

Biofiltration Control of Hydrogen Sulfide 1. Design and Operational Parameters

Laboratory scale biological filter systems for control of hydrogen sulfide (H₂S) in waste gas have been studied and the optimum design and operating parameters determined. Extensive tests have been conducted to evaluate the effect of various filter bed operating parameters such as temperature, retention time, H₂S concentration, and H₂S loading rate. Variable properties of new and used composts such as sulfate content, acidity, and water content have been studied for their influence on H₂S removal efficiency. The effects of compost particle size distribution on system pressure drop and the maximum H₂S elimination capacity were examined. Biofiltration systems containing various types of yard waste compost as the filter material have been observed to remove hydrogen sulfide with efficiencies greater than 99.9 percent for H₂S inlet concentrations in the range from 5 to 2650 ppmv.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.