Articles | Volume 16, issue 6
Atmos. Chem. Phys., 16, 3865–3879, 2016
Atmos. Chem. Phys., 16, 3865–3879, 2016

Research article 23 Mar 2016

Research article | 23 Mar 2016

Oxidative potential of ambient water-soluble PM2.5 in the southeastern United States: contrasts in sources and health associations between ascorbic acid (AA) and dithiothreitol (DTT) assays

Ting Fang1, Vishal Verma2, Josephine T. Bates3, Joseph Abrams4, Mitchel Klein4, Matthew J. Strickland4, Stefanie E. Sarnat4, Howard H. Chang5, James A. Mulholland3, Paige E. Tolbert4, Armistead G. Russell3, and Rodney J. Weber1 Ting Fang et al.
  • 1School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332, USA
  • 2Department of Civil and Environmental Engineering, University of Illinois Urbana-Champaign, Champaign, IL 61801, USA
  • 3School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA
  • 4Department of Environmental Health, Rollins School of Public Health, Emory University, Atlanta, GA 30322, USA
  • 5Department of Biostatistics and Bioinformatics, Rollins School of Public Health, Emory University, Atlanta, GA 30322, USA

Abstract. The ability of certain components of particulate matter to induce oxidative stress through the generation of reactive oxygen species (ROS) in vivo may be one mechanism accounting for observed linkages between ambient aerosols and adverse health outcomes. A variety of assays have been used to measure this so-called aerosol oxidative potential. We developed a semi-automated system to quantify oxidative potential of filter aqueous extracts utilizing the dithiothreitol (DTT) assay and report here the development of a similar semi-automated system for the ascorbic acid (AA) assay. Approximately 500 PM2.5 filter samples collected in contrasting locations in the southeastern US were analyzed for a host of aerosol species, along with AA and DTT activities. We present a detailed contrast in findings from these two assays. Water-soluble AA activity was higher in summer and fall than in winter, with highest levels near heavily trafficked highways, whereas DTT activity was higher in winter compared to summer and fall and more spatially homogeneous. AA activity was nearly exclusively correlated with water-soluble Cu (r  =  0.70–0.94 at most sites), whereas DTT activity was correlated with organic and metal species. Source apportionment models, positive matrix factorization (PMF) and a chemical mass balance method with ensemble-averaged source impact profiles (CMB-E), suggest a strong contribution from traffic emissions and secondary processes (e.g., organic aerosol oxidation or metals mobilization by secondary acids) to both AA and DTT activities in urban Atlanta. In contrast, biomass burning was a large source for DTT activity, but insignificant for AA. AA activity was not correlated with PM2.5 mass, while DTT activity co-varied strongly with mass (r  =  0.49–0.86 across sites and seasons). Various linear models were developed to estimate AA and DTT activities for the central Atlanta Jefferson Street site, based on the CMB-E sources. The models were then used to estimate daily oxidative potential at this site over the 1998–2009 period. Time series epidemiological analyses were conducted to assess daily emergency department (ED) visits data for the five-county Atlanta metropolitan area based on the estimated 10-year backcast oxidative potential. Estimated AA activity was not statistically associated with any tested health outcome, while DTT activity was associated with ED visits for both asthma or wheeze and congestive heart failure. The findings point to the importance of both organic components and transition metals from biomass burning and mobile sources to adverse health outcomes in this region.

Short summary
Ascorbic acid (AA) and Dithiothreitol (DTT) assay measures of water-soluble PM2.5 oxidative potential (OP) are compared in terms of spatiotemporal trends, chemical selectivity, sources, and health impacts based on an epidemiological study with backcast estimated OP. Both assays point to metals from brake/tire wear, but only the DTT assay also identifies organics from combustion. DTT is associated with emergency department visits for asthma/wheeze and congestive heart failure, whereas AA is not.
Final-revised paper