Final Report: Particle Size Distributions of Polycyclic Aromatic Hydrocarbons in the LAB

EPA Grant Number: R827352C013
Subproject: this is subproject number 013 , established and managed by the Center Director under grant R827352
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: Southern California Particle Center and Supersite
Center Director: Froines, John R.
Title: Particle Size Distributions of Polycyclic Aromatic Hydrocarbons in the LAB
Investigators: Miguel, Antonio , Eiguren-Fernandez, Arantza , Sioutas, Constantinos
Institution: University of California - Los Angeles , University of Southern California
EPA Project Officer: Chung, Serena
Project Period: June 1, 1999 through May 31, 2005 (Extended to May 31, 2006)
RFA: Airborne Particulate Matter (PM) Centers (1999) RFA Text |  Recipients Lists
Research Category: Air Quality and Air Toxics , Particulate Matter , Air

Objective:

Topic C: Studies of the Effects of Varying Spatial and Temporal Patterns of Ambient Particulate Matter (PM) and Co-pollutants and Resulting Health Effects with Emphasis on the Role of Atmospheric Chemistry

Epidemiological studies have firmly established that fine particles (F) can adversely affect the health of exposed individuals even at exposure levels at or below the current ambient air standard. Several questions regarding F toxicity remain elusive, including:

  • Which chemical component(s) or class of components of PM are the most hazardous?
  • In addition to the ambient air concentration, what other properties of F are important determinants of health effects?
  • What role does particle size play in F toxicity?
  • How is the toxicity of F affected as it mixes and reacts with gaseous air pollutants and free-radicals during advective atmospheric transport?

For regulatory purposes, to understand how toxin-containing airborne particles are transformed during atmospheric transport, we need to acquire detailed information on their chemical composition, particle size distribution, and concentration during all seasons of the year, both near their emission sources and in locations where humans exposure occurs. The major objective of this research project, complementing other activities described elsewhere in the final reports of the Southern California Particle Center and Supersite (SCPCS), was to acquire information on the effects of season and location on the particle size distribution of polycyclic aromatic hydrocarbons (PAHs) that are defined by the U.S. Environmental Protection Agency (U.S. EPA) as “priority pollutants” in the ambient air of Southern California communities.

Summary/Accomplishments (Outputs/Outcomes):

Methods Development

We developed an analytical protocol for the determination of fifteen U.S. EPA priority pollutant PAHs present in ambient air aerosol. The PAHs are extracted by ultrasonication and quantified using high-performance liquid chromatography (HPLC) with individual fluorescence-excitation wavelength conditions optimized for highest sensitivity. The protocol developed allows the quantification of PAHs present at the pg/m3 range in particles collected from as little as 43 m3 of ambient air (Eiguren-Fernandez and Miguel, 2003). Next, we conducted a field comparison experiment employing different MOUDI impactor configurations to evaluate their sampling performance for the measurement of the size distribution of 15 USEPA priority PAHs in Los Angeles ambient air. There were 24-hour samples collected near Central Los Angeles (high vehicular traffic) and at about 60 km downwind, using collocated MOUDI impactors and classified in three aerodynamic diameter size intervals: ultrafine (UF), accumulation mode, and coarse (C). One MOUDI operated in the conventional mode and one with a vapor trapping system that included an XAD-4 coated annular denuder placed upstream of the impactor and a polyurethane foam (PUF) plug placed in series behind the impactor. PAHs were quantified using the HPLC selective-fluorescence protocol (Eiguren-Fernandez and Miguel, 2003). The results showed that, for both sites, using either sampling system, the size distributions obtained are similar for the less volatile PAHs, but different for the more volatile PAHs. In the central Los Angeles site, the largest PAH fraction was found in the 0–0.18 μm (mode I) size range, typical of primary emissions. At the downwind location, the largest fraction was in the 0.18–2.5 μm (mode II) size range, consistent with an “aged” aerosol (Eiguren-Fernandez, et al., 2003).

Particle Size Distributions: Ultrafine, Accumulation and Coarse Size Ranges

We measured, during all seasons, particle size distributions of 12 priority PAHs (concurrently with elemental carbon (EC), organic carbon (OC), sulfate and nitrate size distributions), from October 2001 to July 2002 in Claremont, CA, a receptor site located about 40km downwind of central Los Angeles. Samples were collected approximately once every week, for 24-hour periods, from midnight to midnight. MOUDI impactors collected samples at 30 LPM which were composited for analysis into monthly periods in three aerodynamic diameter size intervals. For the monthly composites from October to February, the size distributions of the target PAHs are similar. However, from March to July, notable differences are observed: a significant fraction of the PAH mass was found in the C, as compared with the previous period. During the entire 1-year period, the form and shape of the EC size distributions did not vary much and are distinguished by prominent mass in the UF and accumulation size mode. For the individual modes of the major species, the highest Pearson’s correlation coefficients for the variation of temperature with species concentration were found in the UF mode for both sulfate (0.92) and EC (0.90), and in the C for both OC (0.85) and nitrate (0.54). High sulfate correlations are consistent with increased gas-to-particle formation during the warmer months from (precursor) SO2emissions in the Los Angeles and Long Beach seaport areas and, similarly for EC, increased atmospheric transport to Claremont as the season progresses from winter to summer. Although not statistically significant, the correlations were negative for the less volatile or particle phase group, consistent with increased partitioning from the vapor phase with decreasing temperature.

Particle Size Distributions: Aitken Size Range

Measurements in Riverside, California, down to 10 nm aerodynamic diameter (Dp), observed on integrated nocturnal samples (7:00 p.m.–6:30 a.m.), revealed that between 46 and 100% of the mass of particles in the Aitken size range was found in the 10–18 nm size bin (Miguel, et al., 2005). Particles in this size range have high alveolar and upper respiratory region deposition efficiency.

Conclusions:

The analytical protocol developed permits accurate measurement of detailed PAH particle size distributions in ambient air with as little as 43 m3 of sample. Sampling with the regular MOUDI configuration is simpler and thus recommended for measurement of the size distribution of PAHs in both the more volatile and less volatile groups.

While the size distributions of the target PAHs are similar from October to February showing significant UF and accumulation modes, notable differences are observed from March to July when a significant fraction of the PAH mass is found in the C. PAHs found in the Aitken size range in night samples represent a previously unreported particle size range, adding a fourth mode to the typical PAH size distributions found in ambient air. In terms of health significance, this finding is important because of the high deposition efficiency in the upper region and in the alveolar region of the human respiratory tract of particles in the 10–32 nm diameter range. Particles in this size range are able to enter cellular and subcellular targets.

References:

Eiguren-Fernandez A, Miguel AH. Determination of semi-volatile and particulate polycyclic aromatic hydrocarbons in SRM 1649a and PM2.5 samples by HPLC-fluorescence. Polycyclic Aromatic Compounds 2003;23:193-205.

Eiguren-Fernandez A, Miguel A, Jaques P, Sioutas C. Evaluation of a denuder-MOUDI-PUF sampling system to measure the size distribution of semi-volatile polycyclic aromatic hydrocarbons in the atmosphere. Aerosol Science and Technology 2003;37:201-209.

Miguel AH, Eiguren-Fernandez A, Sioutas C, Fine PM, Geller M, Mayo PR. Observations of twelve USEPA priority polycyclic aromatic hydrocarbons in the Aitken size range (10-32 nmD). Aerosol Science and Technology 2005;39(5):415-418.

Technical Report:

Full Final Technical Report (PDF, 6pp., 27.6KB, about PDF)


Journal Articles on this Report : 14 Displayed | Download in RIS Format

Other subproject views: All 14 publications 14 publications in selected types All 14 journal articles
Other center views: All 150 publications 149 publications in selected types All 149 journal articles
Type Citation Sub Project Document Sources
Journal Article Cho AK, Di Stefano E, You Y, Rodriquez CE, Schmitz DA, Kumagai Y, Miguel AH, Eiguren-Fernandez A, Kobayashi T, Avol E, Froines JR. Determination of four quinones in diesel exhaust particles, SRM 1649a and atmospheric PM2.5. Aerosol Science and Technology 2004;38(Suppl 1):68-81. R827352 (Final)
R827352C001 (Final)
R827352C009 (Final)
R827352C013 (Final)
R831861 (2004)
R831861 (2005)
  • Full-text: Taylor & Francis-Full Text PDF
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  • Abstract: Taylor & Francis-Abstract
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  • Journal Article Cho AK, Sioutas C, Miguel AH, Kumagai Y, Schmitz DA, Singh M, Eiguren-Fernandez A, Froines JR. Redox activity of airborne particulate matter at different sites in the Los Angeles Basin. Environmental Research 2005;99(1):40-47. R827352 (Final)
    R827352C001 (Final)
    R827352C013 (Final)
    R827352C014 (Final)
    R832413C003 (2010)
    R832413C003 (Final)
  • Abstract from PubMed
  • Full-text: ScienceDirect-Full Text HTML
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  • Abstract: ScienceDirect-Abstract
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  • Other: ScienceDirect-Full Text PDF
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  • Journal Article de Pereira PA, de Andrade JB, Miguel AH. Determination of 16 priority polycyclic aromatic hydrocarbons in particulate matter by HRGC-MS after extraction by sonication. Analytical Sciences 2001;17(10):1229-1231. R827352 (Final)
    R827352C013 (Final)
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  • Full-text: J-Stage-Full Text PDF
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  • Abstract: J-Stage-First Page
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  • Journal Article de Pereira PA, de Andrade JB, Miguel AH. Measurements of semivolatile and particulate polycyclic aromatic hydrocarbons in a bus station and an urban tunnel in Salvador, Brazil. Journal of Environmental Monitoring 2002;4(4):558-561. R827352 (2004)
    R827352 (Final)
    R827352C013 (Final)
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  • Journal Article Eiguren-Fernandez A, Miguel AH, Jaques PA, Sioutas C. Evaluation of a denuder-MOUDI-PUF sampling system to measure the size distribution of semi-volatile polycyclic aromatic hydrocarbons in the atmosphere. Aerosol Science and Technology 2003;37(3):201-209. R827352 (2004)
    R827352 (Final)
    R827352C013 (Final)
    R827352C014 (Final)
  • Full-text: Taylor&Francis-Full Text PDF
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  • Abstract: Taylor&Francis-Abstract
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  • Journal Article Eiguren-Fernandez A, Miguel AH. Determination of semivolatile and particulate polycyclic aromatic hydrocarbons in SRM 1649a and PM2.5 samples by HPLC-fluorescence. Polycyclic Aromatic Compounds 2003;23(2):193-205. R827352 (2004)
    R827352 (Final)
    R827352C013 (Final)
  • Abstract: Taylor and Francis-Abstract
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  • Journal Article Eiguren-Fernandez A, Miguel AH, Froines JR, Thurairatnam S, Avol EL. Seasonal and spatial variation of polycyclic aromatic hydrocarbons in vapor-phase and PM2.5 in Southern California urban and rural communities. Aerosol Science and Technology 2004;38(5):447-455. R827352 (2004)
    R827352 (Final)
    R827352C009 (Final)
    R827352C013 (Final)
    R831861 (2005)
  • Full-text: Taylor and Francis-Full Text HTML
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  • Abstract: Taylor and Francis-Abstract
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  • Other: Taylor and Francis-Full Text PDF
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  • Journal Article Eiguren-Fernandez A, Avol EL, Thurairatnam S, Hakami M, Froines JR, Miguel AH. Seasonal influence on vapor-and particle-phase polycyclic aromatic hydrocarbon concentrations in school communities located in Southern California. Aerosol Science & Technology 2007;41(4):438-446. R827352 (Final)
    R827352C009 (Final)
    R827352C013 (Final)
    R832413 (2008)
    R832413 (Final)
    R832413C003 (2007)
    R832413C003 (2008)
    R832413C003 (Final)
  • Full-text: Taylor&Francis-Full Text HTML
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  • Abstract: Taylor&Francis-Abstract
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  • Other: Taylor&Francis-Full Text PDF
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  • Journal Article Li N, Venkatesan MI, Miguel A, Kaplan R, Gujuluva C, Alam J, Nel A. Induction of heme oxygenase-1 expression in macrophages by diesel exhaust particle chemicals and quinones via the antioxidant-responsive element. Journal of Immunology 2000;165(6):3393-3401. R827352 (2004)
    R827352 (Final)
    R827352C002 (Final)
    R827352C013 (Final)
  • Abstract from PubMed
  • Full-text: Journal of Immunology-Full Text PDF
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  • Abstract: Journal of Immunology-Abstract and Full Text HTML
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  • Journal Article Li N, Alam J, Venkatesan MI, Eiguren-Fernandez A, Schmitz D, Di Stefano E, Slaughter N, Killeen E, Wang X, Huang A, Wang M, Miguel AH, Cho A, Sioutas C, Nel AE. Nrf2 is a key transcription factor that regulates antioxidant defense in macrophages and epithelial cells: protecting against the proinflammatory and oxidizing effects of diesel exhaust chemicals. Journal of Immunology 2004;173(5):3467-3481. R827352 (2004)
    R827352 (Final)
    R827352C001 (Final)
    R827352C002 (Final)
    R827352C013 (Final)
    R827352C014 (Final)
  • Abstract from PubMed
  • Full-text: Journal of Immunology-Full Text PDF
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  • Abstract: Journal of Immunology-Abstract and Full Text HTML
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  • Journal Article Lu R, Wu J, Turco RP, Winer AM, Atkinson R, Arey J, Paulson SE, Lurmann FW, Miguel AH, Eiguren-Fernandez A. Naphthalene distributions and human exposure in Southern California. Atmospheric Environment 2005;39(3):489-507. R827352 (2004)
    R827352 (Final)
    R827352C013 (Final)
    R827352C015 (Final)
    R831861 (2004)
    R831861 (2005)
  • Full-text: Science Direct-Full Text HTML
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  • Abstract: Science Direct Abstract
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  • Other: Science Direct-Full Text PDF
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  • Journal Article Miguel AH, Eiguren-Fernandez A, Jaques PA, Froines JR, Grant BL, Mayo PR, Sioutas C. Seasonal variation of the particle size distribution of polycyclic aromatic hydrocarbons and of major aerosol species in Claremont, California. Atmospheric Environment 2004;38(20):3241-3251. R827352 (2004)
    R827352 (Final)
    R827352C013 (Final)
    R827352C014 (Final)
  • Full-text: ScienceDirect-Full Text HTML
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  • Abstract: ScienceDirect-Abstract
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  • Other: ScienceDirect-Full Text PDF
    Exit
  • Journal Article Miguel AH, Eiguren-Fernandez A, Sioutas C, Fine PM, Geller M, Mayo PR. Observations of twelve USEPA priority polycyclic aromatic hydrocarbons in the Aitken size range (10-32 nm Dp). Aerosol Science and Technology 2005;39(5):415-418. R827352 (Final)
    R827352C013 (Final)
    R827352C014 (Final)
  • Full-text: Taylor&Francis-Full Text PDF
    Exit
  • Abstract: Taylor&Francis-Abstract
    Exit
  • Journal Article Venkataraman C, Habib G, Eiguren-Fernandez A, Miguel AH, Friedlander SK. Residential biofuels in South Asia:carbonaceous aerosol emissions and climate impacts. Science 2005;307(5714):1454-1456. R827352 (Final)
    R827352C013 (Final)
  • Abstract from PubMed
  • Full-text: Science-Full Text PDF
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  • Abstract: Science-Abstract and Full Text HTML
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  • Supplemental Keywords:

    RFA, Scientific Discipline, Air, Geographic Area, HUMAN HEALTH, particulate matter, Environmental Chemistry, Health Risk Assessment, Air Pollutants, State, mobile sources, Environmental Monitoring, Health Effects, engine exhaust, ambient aerosol, asthma, motor vehicle emissions, epidemiology, human health effects, automotive emissions, particulate emissions, automobiles, automotive exhaust, air pollution, children, human exposure, diesel exhaust particles, PM characteristics, California (CA), allergens, indoor air quality, aerosols, atmospheric chemistry

    Relevant Websites:

    Full Final Technical Report (PDF, 6pp., 27.6KB, about PDF)
    http://www.scpcs.ucla.edu Exit

    Progress and Final Reports:

    Original Abstract
  • 1999
  • 2000
  • 2001
  • 2002 Progress Report
  • 2003 Progress Report
  • 2004 Progress Report

  • Main Center Abstract and Reports:

    R827352    Southern California Particle Center and Supersite

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R827352C001 The Chemical Toxicology of Particulate Matter
    R827352C002 Pro-inflammatory and the Pro-oxidative Effects of Diesel Exhaust Particulate in Vivo and in Vitro
    R827352C003 Measurement of the “Effective” Surface Area of Ultrafine and Accumulation Mode PM (Pilot Project)
    R827352C004 Effect of Exposure to Freeways with Heavy Diesel Traffic and Gasoline Traffic on Asthma Mouse Model
    R827352C005 Effects of Exposure to Fine and Ultrafine Concentrated Ambient Particles near a Heavily Trafficked Freeway in Geriatric Rats (Pilot Project)
    R827352C006 Relationship Between Ultrafine Particle Size Distribution and Distance From Highways
    R827352C007 Exposure to Vehicular Pollutants and Respiratory Health
    R827352C008 Traffic Density and Human Reproductive Health
    R827352C009 The Role of Quinones, Aldehydes, Polycyclic Aromatic Hydrocarbons, and other Atmospheric Transformation Products on Chronic Health Effects in Children
    R827352C010 Novel Method for Measurement of Acrolein in Aerosols
    R827352C011 Off-Line Sampling of Exhaled Nitric Oxide in Respiratory Health Surveys
    R827352C012 Controlled Human Exposure Studies with Concentrated PM
    R827352C013 Particle Size Distributions of Polycyclic Aromatic Hydrocarbons in the LAB
    R827352C014 Physical and Chemical Characteristics of PM in the LAB (Source Receptor Study)
    R827352C015 Exposure Assessment and Airshed Modeling Applications in Support of SCPC and CHS Projects
    R827352C016 Particle Dosimetry
    R827352C017 Conduct Research and Monitoring That Contributes to a Better Understanding of the Measurement, Sources, Size Distribution, Chemical Composition, Physical State, Spatial and Temporal Variability, and Health Effects of Suspended PM in the Los Angeles Basin (LAB)