Determination of Volatile Organic Compounds in the Atmosphere Using Two Complementary Analysis Techniques

ABSTRACT

During a preliminary field campaign of volatile organic compound (VOC) measurements carried out in an urban area, two complementary analysis techniques were applied to establish the technical and scientific bases for a strategy to monitor and control VOCs and photochemical oxidants in the Autonomous Community of the Basque Country. Integrated sampling was conducted using Tenax sorbent tubes and laboratory analysis by gas chromatography, and grab sampling and in situ analysis also were conducted using a portable gas chromatograph. With the first technique, monocyclic aromatic hydrocarbons appeared as the compounds with the higher mean concentrations. The second technique allowed the systematic analysis of eight chlorinated and aromatic hydrocarbons. Results of comparing both techniques, as well as the additional information obtained with the second technique, are included.     

Characterization of Municipal Solid Waste Incineration Residues From Facilities with Different Air Pollution Control Systems

Abstract

Municipal Solid Waste incinerator residues produced in two types of facilities were exhaustively characterized: granulometry, mineralogy, chemical composition, leaching behavior, and elemental distribution as a function of particle size. Air Pollution Control (APC) residues coming from a semi-dry scrubber have shown higher solubility than fly ashes originating in an Electrostatic Precipitator (ESP), as well as higher contents in volatile metals (Cd, Hg). Different metal speciation and distribution as a function of particle size have been found in fly ashes (ESP residues) and APC residues. In APC residues, heavy metals (with the exception of Hg) show a parabolic distribution with maxima in the smallest and largest particles, following the same profile as soluble salts. Metal distribution for APC residues exhibits that metals generally are not associated with silicate aluminate matrix. Results show the effect of adding lime to APC residues in metal speciation and distribution.     

Aerosol Research and Inhalation Epidemiological Study (ARIES): Air Quality and Daily Mortality Statistical Modeling— Interim Results

ABSTRACT

The Aerosol Research and Inhalation Epidemiological Study (ARIES) is an EPRI-sponsored project to collect air quality and meteorological data at a single site in northwestern Atlanta, GA. Seventy high-resolution air quality indicators (AQIs) are used to examine statistical relationships between air quality and health outcome end points. Contemporaneous mortality data are collected for Fulton and DeKalb counties in Georgia. Currently, 12 months of air quality and weather data are available for analysis, from August 1998 through July 1999.

The interim mortality analysis used Poisson regression in generalized additive models (GAMs). The estimated log-linear association of mortality with various AQIs was adjusted for smoothed functions of time and meteorological data. The analysis considered daily deaths due to all nonaccidental causes, deaths to persons 65 years or older, and deaths in each of the two constituent counties. The fine particle effect associated with the four mortality subgroups, using only today (lag 0), yesterday (lag 1), 2-day average (average of today and yesterday), and first difference (today minus yesterday) measurements of the air quality relative to today's number of deaths was positive for lag 0, lag 1, and 2-day average and positive only for decedents at least 65 years of age using first difference. The t values ranged from 0.81 to 1.15 for lag 0, 1.04 to 1.53 for lag 1, 1.10 to 1.66 for 2-day average, and -0.32 to 0.33 for first difference with 346 or 347 days of data. No statistically significant estimate of the linear coefficient was found for the other 14 air quality variables in our interim analysis for the four mortality subgroups. We discuss diagnostics to support these models.

These interim analyses did not include an evaluation of sensitivity to a larger set of lag structures, nonlinear model specifications, multipollutant analyses, alternative weather model and smoothing model specifications, air pollution imputation schemes, or cause-specific mortality indicators, nor did they include a full reporting of model selection or goodness-of-fit indicators. No conclusion can be drawn at this time about whether the findings from subsequent studies have sufficiently greater power to detect effects comparable to those found in other U.S. cities including at least 2 or 3 years of data.     

Biological Removal of Gaseous Ammonia in Biofilters: Space Travel and Earth-Based Applications

ABSTRACT

Gaseous NH₃ removal was studied in laboratory-scale biofilters (14-L reactor volume) containing perlite inoculated with a nitrifying enrichment culture. These biofilters received 6 L/min of airflow with inlet NH₃ concentrations of 20 or 50 ppm, and removed more than 99.99% of the NH₃ for the period of operation (101, 102 days). Comparison between an active reactor and an autoclaved control indicated that NH₃ removal resulted from nitrification directly, as well as from enhanced absorption resulting from acidity produced by nitrification. Spatial distribution studies (20 ppm only) after 8 days of operation showed that nearly 95% of the NH₃ could be accounted for in the lower 25% of the biofilter matrix, proximate to the port of entry. Periodic analysis of the biofilter material (20 and 50 ppm) showed accumulation of the nitrification product NO₃ ^- early in the operation, but later both NO₂ ^- and NO₃ ^- accumulated. Additionally, the N-mass balance accountability dropped from near 100% early in the experiments to ~95 and 75% for the 20- and 50-ppm biofilters, respectively. A partial contributing factor to this drop in mass balance accountability was the production of NO and N₂O, which were detected in the biofilter exhaust.     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

Modeling and Spatially Distributing Forest Net Primary Production at the Regional Scale

Abstract

Forest, agricultural, rangeland, wetland, and urban landscapes have different rates of carbon sequestration and total carbon sequestration potential under alternative management options. Changes in the proportion and spatial distribution of land use could enhance or degrade that area’s ability to sequester carbon in terrestrial ecosystems. As the ecosystems within a landscape change due to natural or anthropogenic processes, they may go from being a carbon sink to a carbon source or vice versa. Satellite image analysis has been tested for timely and accurate measurement of spatially explicit land use change and is well suited for use in inventory and monitoring of terrestrial carbon. The coupling of Landsat Thematic Mapper (TM) data with a physiologically based forest productivity model (PnET-II) and historic climatic data provides an opportunity to enhance field plot-based forest inventory and monitoring methodologies. We use periodic forest inventory data from the U.S. Department of Agriculture (USDA) Forest Service’s Forest Inventory and Analysis (FIA) Program to obtain estimates of forest area and type and to generate estimates of carbon storage for evergreen, deciduous, and mixed-forest classes. The area information is used in an accuracy assessment of remotely sensed forest cover at the regional scale. The map display of modeled net primary production (NPP) shows a range of forest carbon storage potentials and their spatial relationship to other landscape features across the southern United States. This methodology addresses the potential for measuring and projecting forest carbon sequestration in the terrestrial biosphere of the southern United States.     

Air Quality in Selected Megacities

Abstract

About half of the world's population now lives in urban areas because of the opportunity for a better quality of life. Many of these urban centers are expanding rapidly, leading to the growth of megacities, which are often defined as metropolitan areas with populations exceeding 10 million inhabitants. These concentrations of people and activity are exerting increasing stress on the natural environment, with impacts at urban, regional and global levels. In recent decades, air pollution has become one of the most important problems of megacities. Initially, the main air pollutants of concern were sulfur compounds, which were generated mostly by burning coal. Today, photochemical smog—induced primarily from traffic, but also from industrial activities, power generation, and solvents—has become the main source of concern for air quality, while sulfur is still a major problem in many cities of the developing world. Air pollution has serious impacts on public health, causes urban and regional haze, and has the potential to contribute significantly to global climate change. Yet, with appropriate planning megacities can efficiently address their air quality problems through measures such as application of new emission control technologies and development of mass transit systems.

This review is focused on nine urban centers, chosen as case studies to assess air quality from distinct perspectives: from cities in the industrialized nations to cities in the developing world. This review considers not only megacities, but also urban centers with somewhat smaller populations, for while each city—its problems, resources, and outlook—is unique, the need for a holistic approach to complex environmental problems is the same. There is no single strategy to reduce air pollution in megacities; a mix of policy measures will be needed to improve air quality. Experience shows that strong political will coupled with public dialogue is essential to effectively implement the regulations required to address air quality.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Overview and Statistical Considerations

Abstract

Average concentrations of particulate matter with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5) in Steubenville, OH, have decreased by more than 10 μg/m³ since the landmark Harvard Six Cities Study¹ associated the city’s elevated PM_2.5 concentrations with adverse health effects in the 1980s. Given the promulgation of a new National Ambient Air Quality Standard (NAAQS) for PM_2.5 in 1997, a current assessment of PM_2.5 in the Steubenville region is warranted. The Steubenville Comprehensive Air Monitoring Program (SCAMP) was conducted from 2000 through 2002 to provide such an assessment. The program included both an outdoor ambient air monitoring component and an indoor and personal air sampling component. This paper, which is the first in a series of four that will present results from the outdoor portion of SCAMP, provides an overview of the outdoor ambient air monitoring program and addresses statistical issues, most notably autocorrelation, that have been overlooked by many PM_2.5 data analyses. The average PM_2.5 concentration measured in Steubenville during SCAMP (18.4 μg/m³) was 3.4g/m³ above the annual PM_2.5 NAAQS. On average, sulfate and organic material accounted for ～31% and 25%, respectively, of the total PM_2.5 mass. Local sources contributed an estimated 4.6 μg/m³ to Steubenville’s mean PM_2.5 concentration. PM_2.5 and each of its major ionic components were significantly correlated in space across all pairs of monitoring sites in the region, suggesting the influence of meteorology and long-range transport on regional PM_2.5 concentrations. Statistically significant autocorrelation was observed among time series of PM_2.5 and component data collected at daily and 1-in-4-day frequencies during SCAMP. Results of spatial analyses that accounted for autocorrelation were generally consistent with findings from previous studies that did not consider autocorrelation; however, these analyses also indicated that failure to account for autocorrelation can lead to incorrect conclusions about statistical significance.