PERCH Air Quality Study – PAQS Partnership for Environmental Research and Community Health Special thanks to Carl Mohrherr Alan Knowes Staff of OJSES FL-DOH FL-DEP SEARCH

Air Quality Experience Karsten Baumann Michael Bergin Ann Bostrom Carlos Cardelino Bill Chameides Michael Chang Talat Odman Rick Peltier Mohan Turaga Ted Russell Rodney Weber Southern Oxidants Study Fall line Air Quality Study Atlanta Supersite Texas Air Quality Study 2000 Southern Appalachian Mountain Initiative Atlanta Ozone Forecasting Southern Center for the Integrated Study of Secondary Air Pollutants Air Resources Engineering Center

What’s the problem? Is there a problem? Partnership for Environmental Research and Community Health PERCH Mission: to determine if a connection exists between elevated levels of illness in Northwest Florida and the levels of toxic pollutants in the area. Could the air be making people sick or causing premature death?

PERCH Air Quality Study – Phase I Scope: air toxics, ozone, and particulate matter. Identify, compile, and assess existing emissions and ambient air data from US EPA, FL DEP, and private (e.g. SEARCH). Review existing studies (particularly National Air Toxics Assessment and Gulf Coast Ozone Study). Any gaps? Complete a health impacts literature search. Screen for potential health risks due to realized and potential ambient exposures. Design and conduct field pilot study in Phase II.

Deployment of GA Tech’s Mobile Lab Period: 15 July - 14 August, 2003 UWF OLF ELY OJ Semmes ES PNS WAR NVR NAS

Meteorology at OJS

Pollutants at OJS

Pollutants in the Region

Pollutants in the Region Around August 9-10 Weekend Wed Thu Fri Sat Sun Mon Tue Wed

Diurnal Characteristics: Averages, Std.Dev. OLF UWF ELY OJS PNS NAS NVR Convective winds Sporadic SO2 events Bimodal CO and NOy Similar daytime O3 maxima at all sites Less nighttime O3 titration at NAS shoreline Trend to higher PM2.5 mass in southern part

Diurnal Characteristics of Winds OLF ELY PNS OJS NAS NVR Indications for land-sea breeze circulation at shore sites NAS and NVR, with southerly component flow at daytime, northerly at night. Land-sea breeze influence weakens further inland. Indications for “convergence” with synoptic westerlies.

Transport from Local and Distant Sources Wind Frequency Distributions OLF ELY OJS WAR PNS NVR NAS

Transport from Local and Distant Sources Wind Speed OLF ELY OJS WAR PNS NVR NAS

Transport from Local and Distant Sources Sulfur Dioxide (SO2) UWF ELY OLF OJS PNS WAR NVR NAS

Transport from Local and Distant Sources Carbon Monoxide (CO) OLF UWF ELY OJS PNS NVR WAR NAS

Transport from Local and Distant Sources Nitrogen Oxides (NOx & NOy) UWF OLF ELY OJS PNS WAR NVR NAS

Transport from Local and Distant Sources Ozone (O3) ELY OLF OJS WAR PNS NVR NAS

Transport from Local and Distant Sources Fine PM Mass (PM2.5) OLF ELY OJS PNS NVR NAS

Air Toxics from VOC can samples Halogenated HCs F-114 F-11 F-113 CCl4 AVG STD Aromatics Benzene Toluene Ethylbenzene m-xylene p-xylene o-xylene 1,3-butadiene 4-ethyltolene 1,3,5-trimethylbenzene 1,2,4-trimethylbenzene AVG STD

Photochemical Processes Leading to O3 and PM An Assessment of Tropospheric Ozone Pollution, A North American Perspective, NARSTO, National Acad. Press, 2000. NOz SOA

Photochemical Activity Source – Receptor Considerations: O3/NOz as “OPE” Atlanta JST Griffin downwind Elevated regional O3 background reflected in regression’s intercept: higher in Aug 99! At JST higher intercept and slope during Aug ’99 (OPE= 4 vs 3): more efficient P(O3). OPE in air mass arriving at Griffin is likely larger given by upper and lower limits. Lower limit assumes 1st order loss of HNO3 due to surface deposition at k ≈ 0.22 h-1.

OPE Considerations for Pensacola Crude midday OPE is very similar for both sites, indicating moderate OPE. A much more refined analysis is required for true OPE. Intercept indicating relatively low background O3 level.

Secondary organic aerosol (SOA): Organic compounds, some highly oxygenated, residing in the aerosol phase as a function of atmospheric reactions that occur in either gas or particle phases. SOA formation mainly depends on: Emissions & forming potential of precursors aromatics (BTX, aldehydes, carbonyls) terpenes (mono-, sesqui-) other biogenics (aldehydes, alcohols) Presence of other initiating reactants O3, OH, NO3, sunlight, acid catalysts Mechanisms (with half hr to few hr yields): Gas-to-particle conversion/partitioning e.g. terpene oxidation Heterogeneous reactions aldehydes via hydration and polymerization, forming hemiacetal/acetal in presence of alcohols Particle-phase reactions acetal formation catalytically accelerated by particle sulfuric acid (Jang and Kamens, ES&T, 2001)

Particle Composition Monitor “PCM” Channel 1: NH3 Na+, K+, NH4+, Ca+2 Channel 2: HF, HCl, HONO, HNO3, SO2, HCOOH, CH3COOH, (COOH)2 F-, Cl-, NO3-, SO4=, HCOO-, CH3COO-, C2O4= Channel 3: EC, OC, WSOC, “SVOC” Additional higher resolution CO, NO, NOy, O3, PM-mass, and basic meteorology

Preliminary PM2.5 Mass and Composition Data

Preliminary Findings and Outlook Period 7/15-8/14 characterized by frequent precipitation Period has been unseasonably wet for SE-US Leading to low [O3] and [PM2.5] region-wide Land-sea breeze circulation most prominent at shore sites Sea breeze (southerly flow) converging with westerlies on middays Highest [O3] associated with southerly component flow at all sites Highest [PM2.5] with continental air mass during dry period at end OJS predominantly influenced by mobile sources Sporadic SO2 events during morning BL evolution Integrate, further evaluate PILS-IC, VOC, FLDEP, SEARCH data Relate air toxics to other compounds/sources Complete fine PM mass and composition analyses Find resources for transition metals analyses (ICP-MS) Analyze back trajectories for certain episodes Analyze P(O3)/OPE for late episode of regionally high PM Assess fraction of SOA from mass balance Help integrate data for comprehensive exposure/health risk analysis Listen to what is needed!!

Questions, comments, suggestions? Dr. Karsten Baumann kb@eas.gatech.edu Dr. Michael Chang chang@eas.gatech.edu Dr. Ranga Rao rrao@uwf.edu