University at Albany 2000-2004
Program Overview

PM2.5 Technology Assessment and Characterization Study-New York is one of several U.S. EPA "Supersites" intended to provide enhanced measurement data on chemical and physical composition PM and its associated precursors. The science team lead by the University at Albany (PI: Kenneth Demerjian, ASRC/DEAS), includes investigators from ten participating institutions. The science team will collect, analysis and interpret these data to 1) characterize the PM2.5/Co-pollutant complex and its related sources and sinks; 2) support health effects and exposure research; 3) evaluate new measurement technologies and establish their potential for routine monitoring; and establish and demonstrate the use of these data analyses to track mitigation progress and support an accountable air quality management process.

PM2.5, like O3, has a regional component that must be characterized to determine its source and its potential role in the development of mitigation strategies for non-attainment areas. The revised ozone and newly promulgated PM2.5 national ambient air quality standards have placed additional demands on our understanding of the interdependencies of these pollutants and their precursors. This additional knowledge is necessary to implement effective mitigation strategies to achieve these standards. The impact of ineffective, costly emission controls on the economy of New York State and the consequences of environmental benefits lost, present a strong case for the establishment of a EPA PM2.5 "Supersite" in New York State and is reflected in the substantial cost sharing commitment made by the NYS Department of Environmental Conservation (NYSDEC) and NYS Energy Research and Development Authority (NYSERDA) in support of this program.

Abstract

PMTACS-NY is a highly leveraged measurement, technology development and evaluation program designed to address a series of science policy relevant questions that relate to hypotheses to be tested using the extensive data sets collected as part of the program. Primary objectives of the program are the following:

• measure the temporal and spatial distribution of the PM2.5/co-pollutant complex including: SO2, CO, VOCs/air toxics, NO, NO2, O3, NOy, H2CO, HNO3, HONO, PM2.5 (mass, SO4⁼, NO3^-, OC, EC, trace elements), single particle aerosol composition, CN, OH and HO2
  
• monitor the effectiveness of new emission control technologies [i.e. Compressed Natural Gas (CNG) bus deployment and Continuously Regenerating Technology (CRT)]
  
• test and evaluate new measurement technologies and provide tech-transfer of demonstrated operationally robust technologies

Comprehensive measurement of PM2.5 mass, chemical speciation and gaseous precursors will be collected at five monitoring sites located in the New York City metropolitan area and at regional representative locations in upstate NY. These sites include two research regional monitoring sites, Whiteface Mountain (Wilmington, NY) operational since 1973 and Pinnacle State Park (Addison, NY) operational since 1995 and three urban monitoring sites, Mable Dean Bacon (Manhattan, NY or alternate), Intermediate School I.S. 52 (South Bronx, NY) and Queens College/Public School PS 219 (Queens, NY).

These measurement sites constitute the backbone of the PM2.5 "Supersites Network". In addition to standard routine measurements of criteria pollutants and the mandated PM2.5 mass and chemical speciation measurements, these sites will be operating advance instrumentation that will compliment and provide more chemical and temporal specificity of the air quality at these locations. Over the course of this program, these highly relevant measurements, will fill a substantial data need associated with the characterization of the chemical composition of PM2.5 within New York City and the transport-impacted regional background of upstate NY.

Background

Since 1995, the Atmospheric Sciences Research Center, University at Albany has been performing measurements to characterize regional air quality and advance understanding of the precursor relationships pertaining to the formation of photochemical oxidants at two regional research sites, Whiteface Mountain, in Wilmington, NY and Pinnacle State Park in Addison, NY. In 1999 in anticipation of the newly promulgated EPA PM2.5 National Ambient Air Quality Standard (15 mg/m³ annual and 65 mg/m³ 24-hr average), these studies were augmented with PM2.5 measurements. The measurement program was designed to help address major gaps in understanding of the chemical composition of particulate matter in regional environments and their formation pathways. This research effort provided the foundation of the University at Albany response to the EPA solicitation that proposed to establish several so called "PM2.5 Supersites" across the nation¹.

The "Supersites" are intended to provide enhanced measurement data on chemical and physical composition PM and its associated precursors so as

1) to characterize the PM2.5/Co-pollutant complex and its related sources and sinks
2) support health effects and exposure research
3) evaluate new measurement technologies and establish their potential for routine monitoring
4) establish and demonstrate the use of these data analyses to track mitigation progress and support an accountable air quality management process

PM2.5, like O3, has a regional component that must be characterized to determine its source and its potential role in the development of mitigation strategies for non-attainment areas. Chemical speciation measurements of PM2.5 at urban and regional representative sites are essential in support of analyses to help elucidate our understanding of:

1) the chemical and physical processes that couple urban and regional air quality
2) the role that anthropogenic and biogenic sources of VOC, NOx, SO2 and primary particulate play in the production of the PM2.5/co-pollutant complex in time (diurnal, seasonal, and inter annual) and space (local to regional)
3) the effectiveness of emission control technologies on air quality

With billions of dollars spent on control programs and billions more under consideration, suggest a strong need to demonstrate the quantitative effectiveness of future control decisions. The revised ozone and newly promulgated PM2.5 national ambient air quality standards, raise additional questions as to the suspected interdependencies of these pollutants and as to the appropriate mitigation strategies to effectively achieve these standards. The impact of ineffective, costly emission controls on the economy of New York State and the consequences of environmental benefits lost presented a strong case for establishing a EPA PM2.5 "Supersite" program in New York State and was reflected in the substantial cost sharing commitment of the NYS Department of Environmental Conservation, NYS Department of Health, and sponsored fund commitments from NYS Energy Research and Development Authority (NYSERDA), as well as commitments from our academic and industrial partners.

¹Albritton, D.L. and D.S. Greenbaum. Atmospheric Observations: Helping Build the Scientific Basis for Decisions Related to Airborne Particulate Matter. Report of the PM Measurements Research Workshop, Chapel Hill, NC, 1998.

Partners & Sponsors

Principal Investigator
Kenneth L. Demerjian, ASRC / DEAS (University at Albany)

Co-Investigators
G. G. Lala, J. Schwab, V. Mohnen, and U. Roychowdhury, ASRC, University at Albany
P. Galvin, R. Gibbs, D. Felton and T. Lanni, New York State DEC
C. Kolb, M. Zahniser, and D. Worsnop, Aerodyne Research, Inc.
S. Herring, Aerosol Dynamics, Inc.
D. Imre, Brookhaven National Laboratory
P. Hopke, Clarkson University
W. Brune, Penn State University
L. Husain, N. Kim, X. Zhou, NYS Department of Health
R. Weber, Georgia Institute of Technology
J. Zamurs, NYS Department of Transportation
H. Patashnick, Rupprecht and Patashnick Co., Inc.

Co-Sponsors
NYSERDA, EPA, DEC

Organization

Objectives

The primary objectives of the PMTACS-NY program are to

1) measure the temporal and spatial distribution of the PM2.5/co-Pollutant complex including: SO2, CO, VOCs/air toxics, NO, NO2, O3, NOy, H2CO, HNO3, HONO, PM2.5 (mass, SO4⁼, NO3^-, OC, EC, trace elements), single particle aerosol composition, CN, OH and HO2 to support regulatory requirements to develop cost-effective mitigation strategies for PM2.5 and its co-pollutants and to establish trends in the relevant precursor concentrations to assess the impact of recent and future emission reductions in terms of emission control effectiveness and air quality response;

2) monitor the effectiveness of new emission control technologies [i.e. Compressed Natural Gas (CNG) bus deployment and Continuously Regenerating Technology (CRT)] introduced in New York City and its impact on ambient air quality, through mobile platform and fixed site measurements of CO2, CO, NO2, NO, SO2, H2CO, CH4, HONO, CN and aerosol chemical composition; and

3) test and evaluate new measurement technologies and provide tech-transfer of demonstrated operationally robust technologies for network operation in support of the development of process science and observation-based analysis tools and health-based exposure assessments.

Accountability

A suite of gaseous and chemical particulate measurements will be used to track, through direct observation, changes in precursor concentrations in response to implemented control programs, thereby supporting the concept of "Accountability in Air Quality Management Systems" (Demerjian et al., 1995). Considerable expenditures will be necessary to meet the PM2.5 environmental regulation, and the public has the right to ask the scientific and policy communities to evaluate the effectiveness of implemented environmental controls both in terms of meeting air quality standards and anticipated improvements in environmental health. As with any management system, it is reasonable to expect that analytical measures be in place to demonstrate the progress, success and/or failure of the air quality management system.

The measurements will be applied to verify if changes in the PM2.5/co-pollutant complex are detectable with respect to on going or targeted emission control programs. Several opportunities exist with the New York study region to monitor the impact of emission reductions (e.g. Title IV SO2 and NOx stationary source emission controls, heavy-duty diesel particulate emission controls, NOx mobile source emission controls, and fleet fuel switching) on changes in PM2.5/co-pollutant air quality. To be successful, the system must be capable of quantifying the chemical speciation of primary and secondary particulate mass and concentrations of PM precursors. Analysis studies of long-term data records might include for example:

1) tracking concentration changes and trends in SO2, NOy, and NH3 and PM SO4⁼, NO3^-, NH4⁺, and H⁺ in response to Title IV emission reductions

2) tracking concentration changes and trends in PM organics (elemental C, semi-volatile organics) and speciated NOy, in response to VOC and NOx controls implemented under O3 abatement strategies, and diesel control programs.

Science Policy Questions & Hypotheses

PMTACS-NY is designed to address a series of science policy relevant questions that relate to hypotheses to be tested using extensive measurement data collected under the program. The major science policy relevant issues, the identified hypotheses and analyses for testing will likely expand over the course of the program, as measurement data and research findings provide further insights into the characterization PM2.5 and sources.

• Will urban/regional atmospheres have a non-linear response of PM10/PM2.5 mass or composition to changes in precursor source gases (NOx, SO2, VOCs)?
  

H1. Trends in historical and PMTACS measurements of PM mass and SO4⁼ and NO3^- species composition data provide direct evidence for a nonlinear response to Title IV emission reductions. - Correlate trends in seasonal average PM10 SO4⁼ with Title IV SO2 Phase I and Phase II CEM emissions.

H2. PM10/PM2.5 sulfate and nitrate production efficiencies are directly proportional with ozone production efficiencies. - Compare correlation of hourly measurements of O3 vs. (NOy - NOx) and/or O3 vs. CO with PM SO4 vs. (NOy-NOx) and/or PM SO4 vs. CO.

H3. Urban summertime SO4 production is dominated by local SO2 gas to particle transformation. - Calculate the production of SO4 using OH and SO2 measurements and gas phase kinetic rate constant for the OH + SO2 reaction and compare with single particle SO4 measurements (AMS and SPLAT-MS) and continuous PM2.5 sulfate measurements.

• Can chemical source signatures be effectively applied to attribute specific source contributions to monitored species components (e.g. SO4⁼, NO3^- or carbon)?
  

H4. PM Fe/Mg ratios provide an effective signature of oil derived combustion aerosol. - Apply chemical mass balance models, utilizing detailed trace elemental analysis of routine filter mass measurements (24-hr) and special study measurements (6-hr) collected at an urban and regional site.

• Can source attribution and/or multivariate/factor analysis techniques distinguish the contribution of local production versus regionally transported PM2.5 mass?
  

H5. PM V/Se ratios provide an effective signature of coal vs. oil-derived aerosol on the regional scale. - Apply chemical mass balance models, utilizing detailed trace elemental analysis of routine filter mass measurements (24-hr) and special study measurements (6-hr) collected at regional site.

H6. PM As/Se ratios provide an effective signature of mid-western vs. Canadian derived aerosols. (same as above)

H7. Enhanced PM composition and gas phase measurements provide an effective means for distinguishing the contribution of local vs. regional source types/classes within the study region. - Apply factor/multivariate analysis techniques, utilizing detailed trace elemental analysis of routine filter mass measurements (24-hr), special study measurements (6-hr), continuous PM mass and species and gas phase measurements, to distinguish source type/class contributions within the study region.

• What are the sources of PM2.5 affecting NY City/Upstate NY regional air quality? What fraction of the urban/regional PM2.5 mass is semi-volatile organic matter? What is the chemical composition of the semi-volatile organic matter and what are its sources? Are biogenic emissions a significant source of the semi-volatile organic matter PM2.5 mass fraction found in urban/regional atmospheres?
  

H8. Enhanced PM composition and gas phase measurements provide an effective means for distinguishing the contribution of source types/classes within the urban study region. - Apply factor/multivariate analysis techniques, utilizing detailed trace elemental analysis of routine filter mass measurements (24-hr), special study measurements (6-hr), continuous PM mass and species and gas phase measurements, to distinguish urban source type/class contributions.

H9. Biogenic hydrocarbons represent a significant source of the semi-volatile organic matter mass fraction of warm season regional PM2.5 mass. - Correlate collocated measurements of natural hydrocarbon species (e.g. isoprene and a-, b-pinene) and select oxidized carbonyl products with continuous carbon particulate mass measurements (R&P 5400 carbon particulate analyzer), with differential DT TEOM mass, with differential dual ESP TEOM mass measurements.

• Is NH3 concentration a limiting reagent in the production of NH4NO3 in the urban/regional environment? If so, will reductions in SO2 through Title IV controls and proposed reductions in sulfur in fuels result in an increased fraction of PM2.5 mass as nitrate?
  

H10. Changes in ambient PM sulfate mass fraction are anti-correlated with changes in the ambient PM nitrate mass fraction. - Correlate trends in seasonal average measurements of PM mass, SO4, NO3 and NH4 composition at regional and urban sites and their fractional contributions to total PM mass.

• Can the "co-benefits" of on-going NOx/VOC and sulfur control programs be demonstrated through the tracking of selected precursors measurements in PMTACS urban "Supersite" network?
  

H11. Changes in ambient SO2, NOy and VOC are correlated with changes in the locally generated ambient sulfate and nitrate mass fraction. - Correlate trends in seasonal average measurements of SO4/(SO2+SO4), NO3/NOy , their fractional contributions to total PM mass and their correlation with VOC at regional and urban sites.

• Can emission control technology impacts (i.e. D CNG and D CRT emission changes) on ambient air quality (CO, NO, NO2, SO2, H2CO, and PM) be demonstrated and tracked using fast response instrumentation deployed in a mobile platform. Are these impacts observable with a limited fixed site network?

H12. The introduction of CNG-fueled buses in New York City will show measurable reductions of in-use vehicle NO, NO2, SO2, H2CO and PM emissions as compared with their diesel counterparts. - Calculate exhaust emissions of CO, NO, H2CO and CO2 and aerosol chemical species using mobile and open path cross road measurements of in-use standard diesel buses and their CNG replacements along their operational bus routes and at deployment stations.

H13. The introduction of CRT control technology and low sulfur fuels in retrofitted diesel buses in New York City will cause measurable reductions in-use vehicle NO, SO2 and PM emissions as compared with standard diesel buses. - (same as above).

• Are there observable changes in NO, SO2, H2CO and PM air quality as a result of the CNG/CRT bus fleet deployments?

H14. The introduction of CNG-fueled and CRT-retrofitted diesel buses show measurable reductions in ambient NO, SO2, H2CO and PM concentrations at the one or more of the PMTACS urban monitoring sites. - Correlate concentration measurements of NO, SO2, H2CO and PM at the three urban sites with deployment patterns and operations of the CNG/CRT buses fleets.

• Is the EPA designated FRM for PM2.5 mass an exact measurement of the actual mass of atmospheric PM2.5? Does the measurement method have any systematic bias and if so, is it species correlated?

H15. The EPA designated filter based reference method underestimates the actual atmospheric PM2.5 mass by more than 30% as a result of volatile species losses. - EPA FRM mass measurements are to be compared with 1) R&P TEOM mass measurements operating at 30°C with a Nafion dryer and 2) mass measurements from a differential dual ESP TEOM systems. In addition chemical analysis of FRM filters for SO4⁼, NO3^- and total organic will be compared with integrated average data of continuous PM2.5 SO4⁼ and PM2.5 NO3^- (R&P 8400NS) and carbon particulate (R&P 5400) measurements.

H16. Water management and temperature control of existing continuous automated mass, total sulfur and nitrogen species measurement systems represent a major improvement in PM2.5 measurement technology and are the measurement technologies of the future. - Perform collocated comparisons of continuous mass measurements from a standard R&P TEOM at 50°C, a TEOM operating at 30°C with a Nafion dryer, and differential dual ESP TEOM system and continuous PM2.5 SO4⁼and PM2.5 NO3^-(R&P 8400NS) and carbon particulate (R&P 5400) measurements.

H17. Measurements of the optical properties of the atmosphere (light scattering and absorption) using fixed and remote sensing systems provide an effective means for verifying the existence and extent of regional haze and correlated with surface measurements of PM. - Correlate PMTACS-NY PM and optical measurements with satellite measurements from appropriate sensors.

• Are aerosols an effective delivery mechanism for specific gaseous pollutants (e.g. air toxics, oxidants) into the deep lung? What is the role of liquid water in this delivery mechanism?

H18. Quantitative amounts of gaseous pollutants (e.g. PAH, H2CO, xylene, trichlorethylene, etc.) are absorbed on PM and are detectable by Aerosol Mass Spectrometer (AMS) and Single Particle Laser Ablation Time of Flight Mass Spectrometer (SPLAT-MS) analytical techniques. - Correlate continuous (40-min integrated) C2-C10 hydrocarbon and air toxic measurements with PM measurement analyses by thermal volatilization MS and by laser ablation MS.

H19. PM chemical composition varies by aerodynamic size, which in turn varies in time, and with temperature and season resulting in complex variations in chemical inhalation exposures. - Measure chemical species composition as a function of aerosol size, and over the summer and winter season using AMS and SPLAT-MS techniques and apply in a lung inhalation model to estimate relative exposures.

H20. Heterogeneous processes contributed to the oxidizing capacity of the atmosphere resulting in significant production in PM2.5 mass. - Correlate PM SO4⁼ vs. O3 concentrations for high and low relative humidity periods by season. Correlate PM SO4⁼ vs. OH concentrations for high and low relative humidity periods.

• What are the air quality benefits (disbenefits) of a CNG Bus Fleet And CRT Diesel Fleet Deployment?
  

H21. CNG-fueled buses in New York City show measurable reductions of vehicle NO, SO2 and PM emissions, with minimal disbenefits (i.e. increases in H2CO and PM Ultrafine) as compared with their diesel counterparts. - Calculate in-use exhaust emissions of CO, NO, H2CO and CO2 and aerosol chemical species using mobile and open path cross road measurements of standard diesel and CNG buses along bus routes and at deployment stations.

H22. CRT control technology with low sulfur fuels in retrofitted diesel buses in New York City shown measurable reductions of vehicle NO, SO2 and PM emissions, with minimal disbenefits (increases in H2CO and PM Ultrafine) as compared with standard diesel buses. - (same as above).

• Are there observable changes in NO, SO2, H2CO and PM air quality as a result of the CNG/CRT vehicle fleet deployments?

H23. The deployment of CNG-fueled and CRT-retrofitted diesel fleets show measurable reductions in ambient NO, SO2, H2CO and PM concentrations at the one or more of the PMTACS urban monitoring sites. - Correlate concentration measurements of NO, SO2, H2CO and PM at the three urban sites with deployment patterns and operations of the CNG/CRT vehicle fleets.

• Is PM2.5 mass an appropriate surrogate measurement for characterizing regional haze?

H24. Measurements of the optical properties of the atmosphere (aerosol light scattering and absorption) using fixed and remote sensing systems provide an effective means for verifying the existence and extent of regional haze and correlate with surface measurements of PM2.5 mass - Correlate PMTACS-NY PM2.5 mass and optical measurements with satellite measurements from appropriate sensors.

New technology development