2011 Progress Report: Characterization and Source Apportionment

EPA Grant Number: R832415C001
Subproject: this is subproject number 001 , established and managed by the Center Director under grant R832415
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: Rochester PM Center
Center Director: Oberdörster, Günter
Title: Characterization and Source Apportionment
Investigators: Hopke, Philip K.
Current Investigators: Hopke, Philip K. , Gelein, Robert , Prather, Kimberly A.
Institution: Clarkson University , University of Rochester
Current Institution: Clarkson University , University of California - San Diego , University of Rochester
EPA Project Officer: Chung, Serena
Project Period: October 1, 2005 through September 30, 2010 (Extended to September 30, 2012)
Project Period Covered by this Report: July 1, 2010 through June 30,2011
RFA: Particulate Matter Research Centers (2004) RFA Text |  Recipients Lists
Research Category: Health Effects , Air

Objective:

Characterize the nature of the particle-bound reactive oxygen species (ROS) resulting from major biogenic volatile organic compound (VOC) reactions with ozone. 

Progress Summary:

The reactions of ozone with monoterpenes proceed via the formation of multiple oxygen- and carbon-centered free radical species. These radical species are highly reactive and thus, have generally not been measureable. A method for their detection and characterization is needed to preserve these radicals for a sufficiently long time to permit analyzes to be performed. Radical-addition reactions, also called spin trapping techniques, allow the detection of short-lived radicals. This approach has been applied to products from the α-pinene/ozone reaction. Secondary organic aerosol (SOA) from a reaction chamber was collected on quartz fiber filters and extracted. The extracts then were reacted with either 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) or diethyl-(2-methyl-1-oxido-3,4-dihydro-2H-pyrrol-2-yl) phosphonate (DEPMPO) followed by analysis with ion-trap tandem mass spectrometry (MSn) using electrospray ionization (ESI) in the positive scan mode. During the α-pinene ozonolysis a number of intermediate species are formed, some of which are reactive radicals. Proposed formation of two identified carbon- (MW 153 and 125 Da) and four oxygen-centered radicals (MW 157, 167, 183, and 199 Da) is illustrated in Figure 1.  The detection and identification of radicals with molecular weights 199, 183, 153, and 167 Da supported previously identified mechanisms and structures suggestions. A possible reaction mechanism leading to the formation of detected radicals with masses 125 and 157 Da has been reported for first time (Pavlovic and Hopke, 2011). The structures and reactions presented in Figure 1 illustrate possible radical structures and the formation pathways for the first-generation reactions (standard gas-phase chemistry).  The structures whose numbers are highlighted in grey have been confirmed by these studies (Pavlovic and Hopke, 2011).

 
 
Figure 1. Proposed gas-phase reaction mechanism of α-pinene and ozone leading to the formation of detected radicals.
 
In studies of the formation of secondary organic aerosol in indoor air through the ozonolysis of reactive terpenes that are components of household cleaning products, we examined the formation rates of particles and particle-bound ROS at low NOx concentrations. We currently are continuing these studies at realistic NOx concentrations added to the ozone and terpene to explore the role of nitrate radicals in particle and ROS formation. 
 
At the suggestion of the Center’s Science Advisory Committee, we have examined the ROS associated with main and side stream tobacco smoke.  Both research and commercially available cigarettes were tested using mainstream and sidestream smoke generated by a Single Cigarette Smoking Machine. For mainstream smoke from regular and light cigarettes, the total quantities of ROS were 120-150 nmol and 90-110 nmol, respectively. For sidestream smoke, the values were 60-90 nmol and 30-70 nmol for regular and light cigarettes, respectively. The effects of the cigarette filter on the emissions were to reduce the particle mass and particle-phase ROS in the mainstream smoke.
 
Table 1. Particle-bound ROS concentrations measured in previous studies

                                                          Exposed length equals to one Marlboro (red) 
Source Location and Type      ROS Concentration   Inhaled ROS   Mainstream smoke      Sidestream smoke            
                                                    (nmol H2O2/m3-air)       (nmol/hour)               (hours)                          (hours)                                        
Taipei (Taiwan) sidewalk
0.54
0.19
720
355
Singapore (Singapore) ambient
5.71
2.06
68
34
Singapore (Singapore) traffic
15.10
5.44
26
13
Rubidoux, CA (USA) ambient
5.89
2.12
66
33
Flushing, NY (USA) ambient
0.87
0.31
447
220
Rochester, NY (USA) ambient
8.30
2.99
47
23
 

Table 1  summarizes the  particle-bound ROS concentration measured in previous ambient aerosol studies in units of equivalent nmol H2O2  per cubic meter air. According to respiratory study, normal human breathing rate is ~12 breaths per minute with ~half a litter air inhaled per breath. Thus, the ROS concentrations could be converted to the ROS amount inhaled by human breath per hour (also shown in the table). Combined with the data from this study, we can estimate the length of human exposure to ambient air that is equivalent to smoking or being exposed to the sidestream smoke of a Marlboro (red) cigarette. Thus, if one were to continuously breathe ambient air for a total of 2 to 3 days, the resulting ROS exposure would be equivalent to smoking one Marlboro (red) cigarette.  Air heavily impacted by traffic is more polluted, and 1 day of continuous ambient air exposure is equivalent to smoking one cigarette.

Significance to the field:   This work provides a clearer picture of the nature of some short-lived but highly reactive species that are associated with freshly formed secondary organic aerosol.  The work provides a better understanding of the mechanism of formation of SOA and ROS and the nature of the reactive species to which humans are exposed. It also indicates that ROS is associated with cigarette smoking and provides a basis for looking at the relative influence of ambient air on ROS exposure in units of cigarettes smoked.

Relationship to the overall Center goals: We hypothesized that particle-bound ROS might be an important contributor to the health effects resulting from oxidative stress. Thus, understanding the nature of the ROS components, their formation and their reactivity provides a better basis for understanding their potential role in inducing adverse effects.  Also being able to put ambient ROS exposure into the context of a known human health threat (cigarette smoke), further emphasizes the need to reduce exposure to ambient PM.

Relevance to the Agency’s mission: Understanding this oxidative chemistry is important to a fuller understanding of the formation of SOA and associated ROS in the ambient atmosphere. It helps to provide additional insights into the role composition might play in inducing adverse health effects and provides additional information regarding the implications of controlling ozone, a criterion air pollutant.

Potential practical applications:  If ROS associated with biogenic SOA is a driver of adverse health effects, then regulatory action would need to focus more on ozone control as a basis for controlling secondary particulate matter.

Future Activities:

We are working to determine the formation rates of particles and ROS in terpene-ozone reactions in the presence of NOx.


Journal Articles on this Report : 13 Displayed | Download in RIS Format

Other subproject views: All 19 publications 13 publications in selected types All 13 journal articles
Other center views: All 190 publications 156 publications in selected types All 143 journal articles
Type Citation Sub Project Document Sources
Journal Article Lagudu UR, Raja S, Hopke PK, Chalupa DC, Utell MJ, Casuccio G, Lersch TL, West RR. Heterogeneity of coarse particles in an urban area. Environmental Science & Technology 2011;45(8):3288-3296. R832415 (2011)
R832415 (Final)
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  • Journal Article Ogulei D, Hopke PK, Chalupa DC, Utell MJ. Modeling source contributions to submicron particle number concentrations measured in Rochester, New York. Aerosol Science and Technology 2007;41(2):179-201. R832415 (2010)
    R832415 (2011)
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    R832415C001 (2011)
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  • Journal Article Pavlovic J, Hopke PK. Technical note: detection and identification of radical species formed from α-pinene/ozone reaction using DMPO spin trap. Atmospheric Chemistry and Physics Discussions 2009;9(6):23695-23717. R832415 (2009)
    R832415 (2010)
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  • Journal Article Pavlovic J, Hopke PK. Detection of radical species formed by the ozonolysis of α-pinene. Journal of Atmospheric Chemistry 2010;66(3):137-155. R832415 (2011)
    R832415 (Final)
    R832415C001 (2011)
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  • Journal Article Spencer MT, Shields LG, Prather KA. Simultaneous measurement of the effective density and chemical composition of ambient aerosol particles. Environmental Science & Technology 2007;41(4):1303-1309. R832415 (2010)
    R832415 (2011)
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    R832415C001 (2006)
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  • Journal Article Toner SM, Shields LG, Sodeman DA, Prather KA. Using mass spectral source signatures to apportion exhaust particles from gasoline and diesel powered vehicles in a freeway study using UF-ATOFMS. Atmospheric Environment 2008;42(3):568-581. R832415 (2010)
    R832415 (2011)
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  • Journal Article Venkatachari P, Hopke PK, Brune WH, Ren X, Lesher R, Mao J, Mitchell M. Characterization of wintertime reactive oxygen species concentrations in Flushing, New York. Aerosol Science and Technology 2007;41(2):97-111. R832415 (2010)
    R832415 (2011)
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  • Journal Article Venkatachari P, Hopke PK. Development and laboratory testing of an automated monitor for the measurement of atmospheric particle-bound reactive oxygen species (ROS). Aerosol Science and Technology 2008;42(8):629-635. R832415 (2007)
    R832415 (2008)
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  • Journal Article Venkatachari P, Hopke PK. Characterization of products formed in the reaction of ozone with α-pinene: case for organic peroxides. Journal of Environmental Monitoring 2008;10(8):966-974. R832415 (2010)
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  • Journal Article Venkatachari P, Hopke PK. Development and evaluation of a particle-bound reactive oxygen species generator. Journal of Aerosol Science 2008;39(2):168-174. R832415 (2010)
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  • Journal Article Wang Y, Hopke PK, Chalupa DC, Utell MJ. Effect of the shutdown of a coal-fired power plant on urban ultrafine particles and other pollutants. Aerosol Science and Techology 2011;45(10):1245-1249. R832415 (2011)
    R832415 (Final)
    R832415C001 (2011)
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  • Journal Article Wang Y, Hopke PK, Rattigan OV, Xia X, Chalupa DC, Utell MJ. Characterization of residential wood combustion particles using the two-wavelength aethalometer. Environmental Science & Technology 2011;45(17):7387-7393. R832415 (2011)
    R832415 (Final)
    R832415C001 (2011)
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  • Journal Article Yue W, Stolzel M, Cyrys J, Pitz M, Heinrich J, Kreyling WG, Wichmann H-E, Peters A, Wang S, Hopke PK. Source apportionment of ambient fine particle size distribution using positive matrix factorization in Erfurt, Germany. Science of the Total Environment 2008;398(1-3):133-144. R832415 (2007)
    R832415 (2008)
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    R834797 (2016)
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  • Supplemental Keywords:

    RFA, Scientific Discipline, Air, particulate matter, Environmental Chemistry, Health Risk Assessment, Biochemistry, cardiopulmonary responses, chemical characteristics, fine particles, atmospheric particles, airway epithelial cells, airborne particulate matter, human exposure, aerosol composition

    Progress and Final Reports:

    Original Abstract
  • 2006 Progress Report
  • 2007 Progress Report
  • 2008 Progress Report
  • 2009 Progress Report
  • 2010 Progress Report
  • Final Report

  • Main Center Abstract and Reports:

    R832415    Rochester PM Center

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R832415C001 Characterization and Source Apportionment
    R832415C002 Epidemiological Studies on Extra Pulmonary Effects of Fresh and Aged Urban Aerosols from Different Sources
    R832415C003 Human Clinical Studies of Concentrated Ambient Ultrafine and Fine Particles
    R832415C004 Animal models: Cardiovascular Disease, CNS Injury and Ultrafine Particle Biokinetics
    R832415C005 Ultrafine Particle Cell Interactions In Vitro: Molecular Mechanisms Leading To Altered Gene Expression in Relation to Particle Composition