A Review of Time Integrated PM2.5 Monitoring Data in the United States Kenneth L. Demerjian Atmospheric Sciences Research Center University at Albany – SUNY United Nations Economic Commission for European (UNECE) European Monitoring and Evaluation Program (EMEP) Workshop on Particulate Matter (PM) Measurement and Modeling April 20-23, 2004 New Orleans, LA

U.S. EPA PM National Ambient Air Quality Standards Pollutant Standard/Type Particulate Matter (PM 10) 50 mg/m3 annual mean /P&S 150 mg/m3 24-hr /P&S (PM 2.5) 15 mg/m3 annual mean /P&S 65 mg/m3 24-hr /P&S

Daily Distribution of 24-hr PM2.5 Mass from 17 NYC FRM Monitors

NYC 2002 FRM Monitors Annual Distribution of 24-hr PM Mass

PM Speciation Network Samplers Speciation Sampler 24-hr Sample Volume (m3) OC Blank Correction Factor (ug/m3) Met One SASS 9.6 1.4 Anderson RASS 10.4 1.28 R&P 2300 14.4 0.93 URG MASS 16.7 0.56 IMPROVE 32.8 0.4 STN: 1 in three day operation; three simultaneous filters Nylon – IC, Teflon – XRF, Quartz – OC/EC

MET ONE Spiral Aerosol Speciation Sampler (SASSTM)

STN Monitoring Sites: October 2001 – September 2002

Spatial Distribution of STN/FRM Annual PM2 Spatial Distribution of STN/FRM Annual PM2.5 Mass October 2001 – September 2002

STN Annual PM2.5 Mass FRM vs. STN

STN Annual Composition

Spatial Distribution of STN Annual PM2 Spatial Distribution of STN Annual PM2.5_SO4 Mass October 2001 – September 2002

Annual Sulfate Fraction of PM2.5 Mass

Spatial Distribution of STN Annual PM2 Spatial Distribution of STN Annual PM2.5_NO3 Mass October 2001 – September 2002

Annual Nitrate Fraction of PM2.5 Mass

Spatial Distribution of STN Annual PM2 Spatial Distribution of STN Annual PM2.5_NH4 Mass October 2001 – September 2002

Annual Ammonium Fraction of PM2.5 Mass

Spatial Distribution of STN Annual PM2. 5_OC. 1 Spatial Distribution of STN Annual PM2.5_OC*1.4 Mass October 2001 – September 2002

Annual Total Carbon Fraction of PM2.5 Mass

PM2.5 Mass Fraction as Carbon Botanical Garden - Bronx, NY

PM2.5 Mass Fraction as Sulfate Botanical Garden - Bronx, NY

PM2.5 Mass Fraction as Nitrate Botanical Garden - Bronx, NY

PM2.5 Mass Fraction as Carbon Pinnacle State Park - Addison, NY

PM2.5 Mass Fraction as Sulfate Pinnacle State Park - Addison, NY

PM2.5 Mass Fraction as Nitrate Pinnacle State Park - Addison, NY

PM_EC vs. PM_OC*1.4 Seasonal Correlation Botanical Garden, Bronx, NY

PM_EC vs. PM_OC*1.4 Seasonal Correlation Pinnacle State Park Addison, NY

Winter PM2.5 OC vs. EC – Queens College Jan ’96 NEI POA/PEC 1.27 Jan ’99 NEI POA/PEC 2.35

Summer PM2.5 OC vs. EC – Queens College Jul ’96 NEI POA/PEC 1.03 Jul ’99 NEI POA/PEC 0.96

Time-Integrated Measurements What have we learned about the PM air quality issues from time-integrated measurements? Distribution of major PM composition varies regionally Sulfates greater in the east, nitrates greater in the west Organics show limited spatial variability Seasonal variations indicated more nitrates in the winter and more sulfate and organics in the summer

Time-Integrated Measurements What sort of hypothesis testing is being supported by these measurements? Provide long term time series of PM2.5 components Accountability for control strategies and health comes Fuel sulfur rule 2007 diesel emission standard NOx regulation PM nitrate/sulfate changes with reductions in SO2 Process related production of PM components

Time-Integrated Measurements What are the advantages of time-integrated measurements? Provide long term PM speciation data with modest field technician support and modest overall cost (compared to alternatives) Centralized laboratory analyses and QA/QC procedures improves data quality

Time-Integrated Measurements What are the most serious issues by way of representing what is actually in the air? Carbon blank issues and VOC adsorption MDL for metals Time resolution Loss of volatile PM (nitrates and organics)

Time-Integrated Measurements Which issues confound our ability to test hypotheses, to explain PM concentrations? Water and volatility of nitrates and SOA Are critical variables missing that are needed for the support of hypothesis testing/interpretation of mass and species composition measurements? MDL for critical trace elements will limit source apportionment applications EC blanks corrections and MDL will likely limit tracking EC perturbations resulting from diesel emission controls

Time-Integrated Measurements Are the issues/problems intractable in the near term? ICP/MS analysis techniques can provide improved MDLs for trace metals (as compared to XRF) How is confidence in the values created in lieu of standards? Instrument laboratory and field intercomparisons

Acknowledgments This work was supported in part by U.S. Environmental Protection Agency (EPA) cooperative agreement # R828060010 New York State Energy Research and Development Authority (NYSERDA), contract # 4918ERTERES99, New York State Department of Environmental Conservation (NYS DEC), contract # C004210.

Thanks for your attention.