Characterization of Particulate Matter in California

ABSTRACT

The size, composition, and concentration of particulate matter (PM) vary with location and time. Several monitoring/sampling programs are operated in California to characterize PM less than 2.5 and 10 µm in aerodynamic diameter (PM_2.5 and PM₁₀). This paper presents a broad summary of the spatial and temporal variations observed in ambient PM_2.5 and PM₁₀ concentrations in California. Many areas that have high PM₁₀ concentrations also have relatively high PM_2.5 concentrations, and data indicate that a significant portion of the PM₁₀ air quality problem is caused by PM_2.5. To develop effective plans for attaining the ambient PM standards, improved understanding of these unique problems is needed. Since 1989, pollution control efforts—whether specifically targeted for particulate matter or indirectly via controls on gaseous emissions—have caused annual average PM_2.5 and PM₁₀ concentrations to decline at most sites in California.     

Day-of-Week Patterns of Particulate Matter and Its Chemical Components at Selected Sites in California

Abstract

This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) are not only precursors of ozone (O₃) but also of secondary PM, it is useful to know whether the variations by day of week in these precursors are also evident in PM data. Concentrations of PM ≤10 μm (PM₁₀) and ≤2.5[H9262]m in aerodynamic diameter (PM_2.5) were analyzed. PM concentrations exhibit a general weekly pattern, with the maximum occurring late in the workweek and the minimum occurring on weekends (especially Sunday); however, this pattern does not prevail at all sites and areas. PM nitrate (NO₃ ^-) data from Size Selective Inlet (SSI) samplers in the South Coast Air Basin (SoCAB) tend to be somewhat lower on weekends compared with weekdays. During 1988–1991, the weekend average was lower than the weekday average at 8 of 13 locations, with an average decrease of 1%. During 1997–2000, the weekend average was lower than the weekday average at 10 of 13 locations, with an average decrease of 6%. The weekend averages are generally lower than weekday averages for sulfates, organic carbon, and elemental carbon. Because heavy-duty trucks typically represent a major source of elemental carbon, the weekend decrease in heavy-duty truck traffic may also result in a decrease in ambient elemental carbon concentrations.     

Characterization of Major Chemical Components of Fine Particulate Matter in North Carolina

Abstract

This paper presents measurements of daily sampling of fine particulate matter (PM_2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM_2.5 is organic matter, and the major soluble components are sulfate (SO₄ ^2?), ammonium (NH₄ ⁺), and nitrate (NO₃ ^?). NH₄ ⁺ is neutralized mainly by SO₄ ^2? rather than by NO₃ ^?, except in winter when SO₄ ^2? concentration is relatively low, whereas NO₃ ^? concentration is high. The equivalent ratio of NH₄ ⁺ to the sum of SO₄ ^2? and NO₃ ^? is <1, suggesting that SO₄ ^2?and NO₃ ^?are not completely neutralized by NH₄ ⁺. At both rural and urban sites, SO₄ ^2?concentration displays a maximum in summer and a minimum in winter, whereas NO₃ ^?displays an opposite seasonal trend. Mass ratio of NO₃ ^? to SO₄ ^2?is consistently <1 at all sites, suggesting that stationary source emissions may play an important role in PM_2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM_2.5 mass concen trations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM_2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM_2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

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.     

Fugitive Dust Emission Source Profiles and Assessment of Selected Control Strategies for Particulate Matter at Gravel Processing Sites in Taiwan

Abstract

Particles emitted from gravel processing sites are one contributor to worsening air quality in Taiwan. Major pollution sources at gravel processing sites include gravel and sand piles, unpaved roads, material crushers, and bare ground. This study analyzed fugitive dust emission characteristics at each pollution source using several types of particle samplers, including total suspended particulates (TSP), suspended particulate (PM₁₀), fine suspended particulate (PM_2.5), particulate sizer, and dust-fall collectors. Furthermore, silt content and moisture in the gravel were measured to develop particulate emission factors. The results showed that TSP (<100 µm) concentrations at the boundary of gravel sites ranged from 280 to 1290 µg/m³, which clearly exceeds the Taiwan hourly air quality standard of 500 µg/m³. Moreover, PM₁₀ concentrations, ranging from 135 to 550 µg/m³, were also above the daily air quality standard of 125 µg/m³ and approximately 1.2 and 1.5 times the PM_2.5 concentrations, ranging from 105 to 470 µg/m³. The size distribution analysis reveals that mass mean diameter and geometric standard deviation ranged from 3.2 to 5.7 µm and from 2.82 to 5.51, respectively. In this study, spraying surfactant was the most effective control strategy to abate windblown dust from unpaved roads, having a control efficiency of approximately 93%, which is significantly higher than using paved road strategies with a control efficiency of approximately 45%. For paved roads, wet suppression provided the best dust control efficiencies ranging from 50 to 83%. Re-vegetation of disturbed ground had dust control efficiencies ranging from 48 to 64%.     

Characterization of Particulate Matter and Gaseous Emissions of a C-130H Aircraft

Abstract

The gaseous and nonvolatile particulate matter (PM) emissions of two T56-A-15 turboprop engines of a C-130H aircraft stationed at the 123rd Airlift Wing in the Kentucky Air National Guard were characterized. The emissions campaign supports the Strategic Environmental Research and Development Program (SERDP) project WP-1401 to determine emissions factors from military aircraft. The purpose of the project is to develop a comprehensive emissions measurement program using both conventional and advanced techniques to determine emissions factors of pollutants, and to investigate the spatial and temporal evolutions of the exhaust plumes from fixed and rotating wing military aircraft. Standard practices for the measurement of gaseous emissions from aircraft have been well established; however, there is no certified methodology for the measurement of aircraft PM emissions. In this study, several conventional instruments were used to physically characterize and quantify the PM emissions from the two turboprop engines. Emissions samples were extracted from the engine exit plane and transported to the analytical instrumentation via heated lines. Multiple sampling probes were used to assess the spatial variation and obtain a representative average of the engine emissions. Particle concentrations, size distributions, and mass emissions were measured using commercially available aerosol instruments. Engine smoke numbers were determined using established Society of Automotive Engineers (SAE) practices, and gaseous species were quantified via a Fourier-transform infrared-based gas analyzer. The engines were tested at five power settings, from idle to take-off power, to cover a wide range of operating conditions. Average corrected particle numbers (PNs) of (6.4–14.3) × 10⁷ particles per cm³ and PN emission indices (EI) from 3.5 × 10¹⁵ to 10.0 × 10¹⁵ particles per kg-fuel were observed. The highest PN EI were observed for the idle power conditions. The mean particle diameter varied between 50 nm at idle to 70 nm at maximum engine power. PM mass EI ranged from 1.6 to 3.5 g/kg-fuel for the conditions tested, which are in agreement with previous T56 engine measurements using other techniques. Additional PM data, smoke numbers, and gaseous emissions will be presented and discussed.     

A Cost-Effective Weighing Chamber for Particulate Matter Filters

ABSTRACT

Particulate matter (PM) is a ubiquitous air pollutant that has been receiving increasing attention in recent years due in part to the association between PM and a number of adverse health outcomes, including mortality and increases in emergency room visits and respiratory symptoms, as well as exacerbation of asthma and decrements in lung function.^1-5 As a result, the ability to accurately sample ambient PM has become important, both to researchers and to regulatory agencies. The federal reference method for the determination of fine PM as PM_2.5 in the atmosphere recommends that particle-sampling filters be conditioned and weighed in an environment with constant temperature and relative humidity (RH).⁶ It is also recommended that vibration, electrostatic charges, and contamination of the filters from laboratory air be minimized to reduce variability in filter weight measurements. These controls have typically been maintained in small, environmentally controlled “cleanrooms.” As an alternative to constructing an elaborate cleanroom, we have designed, and presented in this paper, an inexpensive weighing chamber to maintain the necessary level of humidity control.     

Characterization of particulate matter for three sites in Kuwait

Many studies have shown strong associations between particulate matter (PM) levels and a variety of health outcomes, leading to changes in air quality standards in many regions, especially the United States and Europe. Kuwait, a desert country located on the Persian Gulf, has a large petroleum industry with associated industrial and urban land uses. It was marked by environmental destruction from the 1990 Iraqi invasion and subsequent oil fires. A detailed particle characterization study was conducted over 12 months in 2004-2005 at three sites simultaneously with an additional 6 months at one of the sites. Two sites were in urban areas (central and southern) and one in a remote desert location (northern). This paper reports the concentrations of particles less than 10 microm in diameter (PM10) and fine PM (PM2.5), as well as fine particle nitrate, sulfate, elemental carbon (EC), organic carbon (OC), and elements measured at the three sites. Mean annual concentrations for PM10 ranged from 66 to 93 microg/m3 across the three sites, exceeding the World Health Organization (WHO) air quality guidelines for PM10 of 20 microg/m3. The arithmetic mean PM2.5 concentrations varied from 38 and 37 microg/m3 at the central and southern sites, respectively, to 31 microg/m3 at the northern site. All sites had mean PM2.5 concentrations more than double the U.S. National Ambient Air Quality Standard (NAAQS) for PM2.5. Coarse particles comprised 50-60% of PM10. The high levels of PM10 and large fraction of coarse particles comprising PM10 are partially explained by the resuspension of dust and soil from the desert crust. However, EC, OC, and most of the elements were significantly higher at the urbanized sites, compared with the more remote northern site, indicating significant pollutant contributions from local mobile and stationary sources. The particulate levels in this study are high enough to generate substantial health impacts and present opportunities for improving public health by reducing airborne PM.     

Current Status of Air Quality Models for Particulate Matter

ABSTRACT

The current status of the mathematical modeling of atmospheric particulate matter (PM) is reviewed in this paper. Simulating PM requires treating various processes, including the formation of condensable species, the gas/ particle partitioning of condensable compounds, and in some cases, the evolution of the particle size distribution. The algorithms available to simulate these processes are reviewed and discussed. Eleven 3-dimensional (3-D) Eulerian air quality models for PM are reviewed in terms of their formulation and past applications. Results of past performance evaluations of 3-D Eulerian PM models are presented. Currently, 24-hr average PM_2.5 concentrations appear to be predicted within 50% for urban-scale domains. However, there are compensating errors among individual particulate species. The lowest errors tend to be associated with SO₄ ^2-, while NO₃ ^-, black carbon (BC), and organic carbon (OC) typically show larger errors due to uncertainties in emissions inventories and the prediction of the secondary OC fraction. Further improvements and performance evaluations are recommended.     

Spatial Variability of Different Fractions of Particulate Matter within an Urban Environment and between Urban and Rural Sites

ABSTRACT

The spatial variability of different fractions of particulate matter (PM) was investigated in the city of Basel, Switzerland, based on measurements performed throughout 1997 with a mobile monitoring station at six sites and permanently recorded measurements from a fixed site. Additionally, PM₁₀ measurements from the following year, which were concurrently recorded at two urban and two rural sites, were compared.

Generally, the spatial variability of PM₄, PM₁₀, and total suspended particulates (TSP) within this Swiss urban environment (area = 36 km²) was rather limited. With the exception of one site in a street canyon next to a traffic light, traffic density had only a weak tendency to increase the levels of PM. Mean PM₁₀ concentration at six sites with different traffic densities was in the range of less than ±10% of the mean urban PM₁₀ level. However, comparing the mean PM levels on workdays to that on weekends indicated that the impact of human activities, including traffic, on ambient PM levels may be considerable.

Differences in the daily PM₁₀ concentrations between urban and more elevated rural sites were strongly influenced by the stability of the atmosphere. In summer, when no persistent surface inversions exist, differences between urban and rural sites were rather small. It can therefore be concluded that spatial variability of annual mean PM concentration between urban and rural sites in the Basel area may more likely be caused by varying altitude than by distance to the city center.     

Hot Filter/Impinger and Dilution Sampling for Fine Particulate Matter Characterization from Ferrous Metal Casting Processes

Abstract

A study using two stack-sampling methodologies for collecting particulate matter (PM) emissions was conducted using a hot filter followed by a cold impinger sampling train and a dilution sampler. Samples were collected from ferrous iron metal casting processes that included pouring molten iron into a sand mold containing an organic binder, metal cooling, removal of the sand from the cooled casting (shakeout), and postshakeout cooling. The shakeout process contributed more to PM emissions than the metal pouring and cooling processes. Particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5) mass emissions for the entire casting cycle ranged from 3.4 to 4.7 lb/t of metal for the hot filter/impinger method and from 0.8 to 1.8 lb/t of metal for the dilution method. Most of the difference was due to PM captured by the impingers, much of which was probably dissolved gases rather than condensable vapors. Of the PM fraction captured by the impingers, 96–98% was organic in nature. The impinger PM fraction contributed 32–38% to the total suspended particle mass and caused a factor of 2–4 positive bias for PM_2.5 emissions. For the pouring and cooling processes only, the factor increased to over seven times.     

A Pilot Indoor-Outdoor Study of Organic Particulate Matter and Particulate Mutagenicity

Abstract

Many large metropolitan areas experience elevated concentrations of ground-level ozone pollution during the summertime “smog season”. Local environmental or health agencies often need to make daily air pollution forecasts for public advisories and for input into decisions regarding abatement measures and air quality management. Such forecasts are usually based on statistical relationships between weather conditions and ambient air pollution concentrations. Multivariate linear regression models have been widely used for this purpose, and well-specified regressions can provide reasonable results. However, pollution-weather relationships are typically complex and nonlinear—especially for ozone—properties that might be better captured by neural networks. This study investigates the potential for using neural networks to forecast ozone pollution, as compared to traditional regression models. Multiple regression models and neural networks are examined for a range of cities under different climate and ozone regimes, enabling a comparative study of the two approaches. Model comparison statistics indicate that neural network techniques are somewhat (but not dramatically) better than regression models for daily ozone prediction, and that all types of models are sensitive to different weather-ozone regimes and the role of persistence in aiding predictions.     

Determination of Levoglucosan in Atmospheric Fine Particulate Matter

Abstract

A microanalytical method suitable for the quantitative determination of the sugar anhydride levoglucosan in low-volume samples of atmospheric fine particulate matter (PM) has been developed and validated. The method incorporates two sugar anhydrides as quality control standards. The recovery standard sedoheptulosan (2,7-anhydro-β-D-altro-heptulopyranose) in 20 μL solvent is added onto samples of the atmospheric fine PM and aged for 1 hr before ultrasonic extraction with ethylacetate/ triethylamine. The extract is reduced in volume, an internal standard is added (1,5-anhydro-D-mannitol), and a portion of the extract is derivatized with 10% by volume N-trimethylsilylimidazole. The derivatized extract is analyzed by gas chromatography/mass spectrometry (GC/MS). The recovery of levoglucosan using this procedure was 69 ± 6% from five filters amended with 2 μg levoglu-cosan, and the reproducibility of the assay is 9%. The limit of detection is ～0.1 μg/mL, which is equivalent to ～3.5 ng/m³ for a 10 L/min sampler or ～8.7 ng/m³ for a 4 L/min personal sampler (assuming 24-hr integrated samples). We demonstrated that levoglucosan concentrations in collocated samples (expressed as ng/m³) were identical irrespective of whether samples were collected by PM with aerodynamic diameter ≤2.5 μm or PM with aerodynamic diameter ≤10 μm impactors. It was also demonstrated that X-ray fluorescence analysis of samples of atmospheric PM, before levoglucosan determinations, did not alter the levels of levoglucosan.     

Determination of Fine Particulate Semi-Volatile Organic Material at Three Eastern U.S. Sampling Sites

ABSTRACT

Correct assessment of fine particulate carbonaceous material as a function of particle size is, in part, dependent on the determination of semi-volatile compounds, which can be lost from particles during sampling. This study gives results obtained for the collection of fine particulate carbonaceous material at three eastern U.S. sampling sites [Philadelphia, PA; Shenandoah National Park, VA; and Research Triangle Park (RTP), NC] using diffusion denuder technology. The diffusion denuder samplers allow for the determination of fine particulate organic material with no artifacts, due to the loss of semi-volatile organic particulate compounds, or collection of gas-phase organic compounds by the quartz filter during sampling. The results show that an average of 41, 43, and 59% of fine particulate organic material was lost as volatilized semi-volatile organic material during collection of particles on a filter at Philadelphia, RTP, and Shenandoah, respectively. The particle size distribution of carbonaceous material retained by a filter and lost from a filter during sampling was obtained for the samples collected at Philadelphia and Shenandoah. The carbonaceous material retained by the particles during sampling was found predominantly in particles smaller than 0.4 μm in aerodynamic diameter. In contrast, the semi-volatile organic material lost from the particles during sampling had a mass median diameter of ~0.5 μm.     

Applicability of the Mass Concentration Standards for Particulate Matter in Alaskan Areas

The so-called “Six Month Study” of the air toxics problem in the United States was initiated in November 1983 by the U.S. Environmental Protection Agency. The study focused on the magnitude, nature, and distribution of the problem—three major issues that were felt to be most useful to policy makers as they attempted to define the scope and direction of a national program for controlling toxic air pollutants. The following paper is based on a draft staff report on the study released for review in September 1984. The report has not been formally released by the U.S. EPA; a final report is due by late spring of 1985.     

Oxalic Acid in PM2.5 Particulate Matter in California

ABSTRACT

Ambient air monitoring for organic acids in PM₂₅ was conducted at several locations in California. During the study, it was found that oxalic acid (ethanedioc acid) was the most abundant organic acid found in the PM_{2 5} fraction. Samples from Azuza (in southern California), San Jose (in the San Francisco Bay area), and Fresno (in central California), a PM_2.5 Super Site, were collected in 1999 and analyzed. The results for oxalic acid concentrations during this monitoring effort are presented.     

Assessment of Human Exposure to Ambient Particulate Matter

ABSTRACT

Recent epidemiological studies have consistently shown that the acute mortality effects of high concentrations of ambient particulate matter (PM), documented in historic air pollution episodes, may also be occurring at the low to moderate concentrations of ambient PM found in modern urban areas. In London in December 1952, the unexpected deaths due to PM exposure could be identified and counted as integers by the coroners. In modern times, the PM-related deaths cannot be as readily identified, and they can only be inferred as fractional average daily increases in mortality rates using sophisticated statistical filtering and analyses of the air quality and mortality data. The causality of the relationship between exposure to ambient PM and acute mortality at these lower modern PM concentrations has been questioned because of a perception that there is little significant correlation in time between the ambient PM concentrations and measured personal exposure to PM from all sources (ambient PM plus indoor-generated PM).

This article shows that the critical factor supporting the plausibility of a linear PM mortality relationship is the expected high correlation in time of people's exposure to PM of ambient origin with measured ambient PM concentrations, as used in the epidemiological time series studies. The presence of indoor and personal sources of PM masks this underlying relationship, leading to confusion in the scientific literature about the strong underlying temporal relationship between personal exposure to PM of ambient origin and ambient PM concentration. The authors show that the sources of PM of non-ambient origin operate independently of the ambient PM concentrations, so that the mortality effect of non-ambient PM, if any, must be independent of the effects of the ambient PM exposures.