New York PM Supersite Update: What Have We Learned/Where Do We Need - - PowerPoint PPT Presentation

New York PM Supersite Update: What Have We Learned/Where Do We Need to Go? NYSERDA EMEP

October 7, 2003

Kenneth L. Demerjian Atmospheric Sciences Research Center University at Albany State University of New York

U.S. EPA PM Supersites Program

• A strategic ambient monitoring research program designed

to develop, deploy and evaluate measurement technologies for the monitoring of the physical and chemical characteristics of particulate matter (PM) and its relationship to PM mass as measured by the Federal Reference Method (FRM).

• The program consists of two Phase I and seven Phase II

sites distributed across the country: New York, Baltimore, Pittsburgh, St. Louis, Houston, Fresno and Los Angeles.

Trends (54) Supplemental (~215 sites currently known) Supersites Daily Sites IMPROVE IMPROVE Protocol Castnet conversion Deploy in 2002 Deploy in 2003

Current/Planned Urban & Rural PM2.5 Speciation Networks

SS SS

SS

SS SS SS SS SS 01/02

PMTACS-NY Measurement Sites

Program Objectives

5 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), aerosol size distribution, single

particle aerosol composition, CN, OH and HO2. 5 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. 5 Test and evaluate new measurement technologies and provide tech­transfer of demonstrated operationally robust technologies for network operation.

PMTACS­NY Science Policy Relevant Highlights

• Testing and evaluation of new measurement instrumentation

and technology transfer.

• Air quality issues associated with CNG powered and retrofit

diesel control technologies (DF­CRT).

• PM2.5 Chemical and Physical Characterization in support of

SIP development and demonstrating accountability in air quality management.

• Benefits of the introduction of low sulfur fuels on local sulfate

production.

Testing and evaluation of new measurement instrumentation and technology transfer

• Testing and Evaluation of R&P TEOM based

PM2.5 Mass Monitoring Systems

• Testing and Evaluation of Semi­continuous PM2.5

Sulfate Measurement Technology

• Testing and Evaluation of Semi­continuous PM2.5

Nitrate Measurement Technology

• Testing and Evaluation of ARI, Aerosol Mass

Spectrometer (AMS)

EMEP Poster Session

• Intercomparison of Semi-Continuous Particulate Sulfate and

Nitrate Measurement Technologies at a New York State Urban and Rural Location; Olga Hogrefe, F. Drewnick, J. J. Schwab, K. Rhoads, S. Peters and K. L. Demerjian

• Semi-Continuous PM2.5 Sulfate and Nitrate Measurements In New

York City and Whiteface Mountain; Oliver V. Rattigan, D. H. Felton, J. J. Schwab, U.K. Roychowdhury and K. L. Demerjian

• Aerosol Size Distributions: A Comparison of Measurements From

Urban and Rural Sites; G. Garland Lala, O. Hogrefe and K. L. Demerjian

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EMEP Poster Session (continued)

• Measurements of Carbon Particulate Matter in the Adirondack

Region of Upstate New York; U. K. Roychowdhury, D. H. Felton, J. Schwab and K. L. Demerjian

• Aerosol Laboratory Evaluations of PM2.5 Measurement

Technologies; Olga Hogrefe, J.J. Schwab, G.G. Lala, O. V. Rattigan, J. Ambs and K.L. Demerjian

• Recent Developments in the Field Evaluation of TEOM Based

PM2.5 Monitoring Technologies; James J. Schwab, D. H. Felton, J. Ambs, J. Spicer and K.L. Demerjian

CNG/CRT Emission Perturbation Experiment (CEPEX)

Characterize new and existing engine technologies used by NYC Metropolitan Transit Authority (MTA). ‘Traditional’ Diesel: 6V92 & Series 50 Retrofit (Diesel Particulate Filter - CRT) Compressed Natural Gas (CNG) Hybrid Diesel Electric (Diesel Generator, Electric Motor) Sample heavy duty vehicles using ARI Mobile Lab Low Sulfur Fuel Power Plant Plume Characterization Tractor Trailer Transfer Station (Hunt’s Point) Examine Airport Emissions/ Urban Air Quality

In­Use Emission Characterization of CNG powered and Retrofit (DF­CRT) Controlled and Standard Diesel

• Show significant PM emission reductions in CNG and

DF-CRT retrofit technology

• Show increases in NO2/NOx in DF-CRT
• Show increased H2CO and CH4 emissions in CNG

powered vehicles

• Show PM Organic emission as a significant contributor to

ambient PM

• Show lower SO2 emission in low sulfur fueled vehicles,

little change on primary PM sulfate (low)

• Show NOx emissions across the sampled vehicle

population remain an issue

~ 60% Reduction in NRPM

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• Diesel bus exhaust

spectrum is an average

• f PM exhaust MS

sampled during (CEPEX)

• Lubricant oil and diesel

fuel spectra were

• btained from lab

aerosol measurements

Typical Diesel PM Organic & Sulfate Measurements Averaged over a Chase Event

Average Organic and Sulfate Exhaust Only

Diesel Vehicle Chase event: in­plume ­ background

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Queens College July 2001

Average Size Distribution Over Campaign

Typical Size Distributions Sulfate: 1 mode @ 440 nm Nitrate: 1 mode @ 450 nm Ammonium: 1 mode @ 400 nm Organics: 2 modes @ 70/300 nm Sulfate/Nitrate internally mixed Ammonium: mixed with organic interferents/fragments

100 80 60 40 20 Inlet Transmission Efficiency / %

2 3 4 5 6 7 8

0.1

2 3 4 5 6 7 8

1

2

Aerodynamic Particle Diameter / µm 8 6 4 2 dM/d log Dp / µg/m3 µm Nitrate Sulfate Ammonium Organics

Inlet Transmission Function

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• weak diurnal cycle: no shifts in mode

diameters, small changes in intensities

• During morning rush­hour:

extraordinary intensive small particle mode of the organic particles:

Ambient Diurnal Cycles QC 2001

Size Distributions

6 5 4 3 2 1 dM/d log Dp / µ g/m

0.1

1

Aerodynamic Diameter / µm Sulfate Nitrate Organics

1 h

6 5 4 3 2 1 dM/d log Dp / µ g/m

0.1

1

Aerodynamic Diameter / µm

7 h

6 5 4 3 2 1 dM/d log Dp / µ g/m

0.1

1

Aerodynamic Diameter / µm

13 h

6 5 4 3 2 1 dM/d log Dp / µ g/m

0.1

1

Aerodynamic Diameter / µm

19 h

40 35 30 25 Fraction / %

0:00 - 1:00 1:00 - 2:00 2:00 - 3:00 3:00 - 4:00 4:00 - 5:00 5:00 - 6:00 6:00 - 7:00 7:00 - 8:00 8:00 - 9:00 9:00 - 10:00 10:00 - 11:00 11:00 - 12:00 12:00 - 13:00 13:00 - 14:00 14:00 - 15:00 15:00 - 16:00 16:00 - 17:00 17:00 - 18:00 18:00 - 19:00 19:00 - 20:00 20:00 - 21:00 21:00 - 22:00 22:00 - 23:00 23:00 - 24:00

Fraction in small particle mode

Whiteface Mountain July 2002

Average Size Distribution Over the Campaign

Average mode diameters and distribution widths for the campaign: Sulfate: Dmode: 451.55 nm width: 541.31 nm Nitrate: Dmode: 398.10 nm width: 627.43 nm Organics: Dmode: 376.32 nm width: 535.32 nm m43: Dmode: 368.35 nm width: 537.19 nm m44: Dmode: 417.60 nm width: 614.26 nm

150 100 50 dM/d log Dp / a.u.

3 4 5 6 7 8 9

100

2 3 4 5 6 7 8 9

1000

2

Aerodynamic Diameter / nm

Sulfate Nitrate Ammonium Organics m18 m43 m44

wvutsronmlihgfedcbaTMA Sulfate Emission Ratio versus Bus Type ∆Sulfate /∆CO2

0.05 0.04 0.03 0.02 0.01 0.00

• 0.01
• 0.02

(µg/m

3

)/ppm

6V92 Cummins Series 50 CRT Hybrid CNG Diesel CNG SB OB Truck Dirty Car Tunnel MTA Buses Non-MTA Buses Other Buses 2 44 2 2 10 36 3 4 22 7 1 2

∆ (Sulfate)/∆ CO2

N =48

MTA buses (using low sulfur fuel) emit less sulfate than commercial diesel vehicles

Why is it important to characterize PM in ambient air?

¾ Determination of Composition as a Function Mass and Particle Size

• provides insight into source attribution and mitigation

strategies

• improves identification of health based cause­effect

relationships ¾ Determination of Urban/Rural Differences in PM Composition

• provides insight into contributions from local versus

transported PM

• provides insight into primary and secondary PM

contributions in regional environments and there contribution to welfare effects (e.g. visibility and climate)

FRM PM2.5 Mass Spatial Correlation

QCII - FRM, µg/m3

Queens College and IS­52

80 60 40 20

• 0.6886 + 0.9342*x

Multiple R2 = 0.9398

2001­2002

10 30 50 70 IS52 - FRM, µg/m3

FRM PM2.5 Mass Spatial Correlation

PS59-FRM, µg/m3

PS­59 and IS­52

80 60 40 20 2.506 + 0.9791*x Multiple R2 = 0.9303

2001­2002

10 30 50 70 IS52-FRM, µg/m3

PM2.5 Sulfate Mass Spatial Correlation

PS-219 Queens PM2.5_SO4, µg/m3 25 20 15 10 5 April 2001 - October 2002

• 0.07566 + 0.9926*x

Multiple R2 = 0.95 5 10 15 20 25 IS-52 Bronx PM2.5_SO4, µg/m3

PM2.5 Nitrate Mass Spatial Correlation

PS-219 Queens PM2.5_NO3, µg/m3 8 6 4 2 April 2001 - October 2002 0.1806 + 0.8795*x Multiple R2 = 0.8642 1 3 5 7 9 IS-52 Bronx PM2.5_NO3, µg/m3

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PM2.5 Ammonium Mass Spatial Correlation

PS-219 Queens PM2.5_NH4, µg/m3 8 6 4 2 April 2001 - October 2002 0.04964 + 0.9746*x Multiple R2 = 0.920 1 3 5 7 9 IS-52 Bronx PM2.5_NH4, µg/m3

PM2.5 Organic Mass Spatial Correlation

PS-219 Queens PM2.5_OC*1.4, µg/m3 50 30 10

• 10

July 7, 2002 Canadian Smoke Event

April 2001 - October 2002

• 0.3252 + 0.7873*x

Multiple R2 = 0.800

• 10

10 20 30 40 50 60 IS-52 Bronx PM2.5_OC*1.4, µg/m3

PS-219 Queens PM2.5_EC, µg/m3

PM2.5 Elemental Carbon Mass Spatial Correlation

2.5 2.0 1.5 1.0 0.5 0.0 April 2001 - October 2002 0.2791 + 0.3341*x Multiple R2 = 0.2144 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 IS-52 Bronx PM2.5_EC, µg/m3

PM2.5 Crustal Mass Spatial Correlation

PS-219 Queens PM2.5_Crustal, µg/m3 4 3 2 1 April 2001 - October 2002 0.05438 + 0.8764*x Multiple R2 = 0.665 1 2 3 4 IS-52 Bronx PM2.5_Crustal, µg/m3

0.00 5.00 10.00 15.00 20.00 25.00 1 2 3 4 5 6 7 8 9 10 11 12 month PM_species, ug/m3 Ammonium Nitrate Sulfate Crustal EC_niosh OC*1.4

PM2.5 Composition by Month

Queens, NY September 2000 – October 2002

1 2 3 4 5 6 7 8 9 10 11 12 month 0.0 0.1 0.2 0.3 0.4 0.5 PM_SO4 Fraction of Total PM2.5 Bronx, NY June 2000-October 2002

Sulfate Fraction of PM2.5 Mass

Organic Fraction of PM2.5 Mass

PM_OC*1.4 Fraction of Total PM2.5 1.1 0.9 0.7 0.5 0.3 0.1

• 0.1

Bronx, NY June 2000 - October 2002 1 2 3 4 5 6 7 8 9 10 11 12 month

Nitrate Fraction of PM2.5

1 2 3 4 5 6 7 8 9 10 11 12 month 0.0 0.1 0.2 0.3 NO3.frac

Benefits of the introduction of low sulfur fuels on local sulfate production

• Significant reductions in SO2 emission are observed in low

sulfur fueled vehicles

• Production of PM sulfate from the reaction of OH and SO2

can constitute a significant contribution to observed ambient sulfate concentrations

• Most observed urban SO2 concentrations are likely due to

local generation from fossil fuel burning

• Federally mandated low sulfur fuel rules for mobile

sources should have PM mitigation benefits

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Hour 0.0 0.5 1.0 1.5 Sulfate OH Production Rate, ug/m3 hr-1

Diurnal Box Plot of SO4 Production Rates, µg/m3 hr­1as Calculated from (OH­SO2 reaction)

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0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0:00 3:00 6:00 9:00 12:00 15:00 18:00 21:00 0:00

Time of Day P(H2SO4) (ug/m3/hr)

1 2 3 4 5 6 7

Cumulative P(H2SO4 ) (ug/m3 )

P(H2SO4) Cumulative P(H2SO4)

Diurnal variation of H2SO4 production (OH+SO2)

• H2SO4 production from OH + SO2 is about 5.1 µg/m3/day.

10 min avg. data

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A Particle Production Event

Event # 3 – Comparison of Particle Production Rates:

Mass Concentration / µg/m

3

14

AMS Sulfate 8400S Sulfate

12 10 8 6 4 2 06:00

Average Sulfate Particle Production Rates: PILS = 0.873 µg/m3h; AMS = 0.844 µg/m3h; R&P 8400S = 0.464 µg/m3h

3

PILS Sulfate

July 17

09:00 12:00 15:00 18:00 21:00 00:00 Time

ec.niosh

PM2.5 EC Bronx, NY 2000­2002

4 3 2 1 1 2 3 4 5 6 7 8 9 10 11 12 month

Planned Activities June 2003 – December 2004

• Winter Field Intensive Queens College: January 15 –

February 15, 2004

• Participation in New England Air Quality Study: Summer

2004

• Intercomparison Studies of FRM and FDS­ and ESP-

TEOM systems

• Aerosol Laboratory Studies:

– R&P 8400N yield issues – Filter artifact studies – De­ammoniation of FRM filters – Secondary organics

Future Needs

• Extension of Supersite Monitoring to Support:

– PM model development and evaluation – Upcoming SIP calls – Health Effects Studies – Accountability Paradigm – Regional Transport of PM2.5, O3 and Precursors and Related Attribution Studies

Acknowledgements

• Research Team:

– ASRC: J. Schwab, U. Roychowdhury, G. Lala, F. Drewnick, O. Hogrefe,

• Y. Li, J. Spicer, G. Schmidt, R. Lamica, K. Eckhardt, T. Coleman, and V.

Mohnen – Graduate Students: C. Bai, S. Peters, M. Tang, and C. Cai – NYS DEC: D. Felton, P. Galvin, G. Boynton, T. Lanni, S. Tang, and B. Frank – PSU: W. Brune, X. Ren, R. Lesher – NYS DOH: L. Husain, X. Zhou – Aerodyne Research: D.Worsnop, J. Jayne, M. Canagaratna, S.Herndon

• Sponsors:

– NYSERDA, U.S. EPA & NYS DEC

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Publications Submitted

Development and Operation of an Aerosol Generation, Calibration and Research Facility Olga Hogrefe, G. Garland Lala, James J. Schwab, Frank Drewnick and Kenneth L. Demerjian Atmospheric Sciences Research Center, University at Albany, State University of New York, 251 Fuller Road, Albany, NY 12203 (Submitted to Aerosol Science & Technology). Measurement of Ambient Aerosol Composition during the PMTACS-NY 2001 using an Aerosol Mass Spectrometer - Part I: Mass Concentrations Frank Drewnick, James J. Schwab, John T. Jayne, Manjula Canagaratna, Douglas R. Worsnop, Kenneth L. Demerjian Atmospheric Sciences Research Center, State University of New York, 251 Fuller Road, Albany, NY 12203, USA (F.D., J.J.S., K.L.D.) Center for Aerosol and Cloud Chemistry, Aerodyne Research Inc, 45 Manning Road, Billerica, MA 01821­3976 (J.T.J., M.C., D.R.W.) (Submitted to Aerosol Science & Technology). Measurement of Ambient Aerosol Composition during the PMTACS-NY 2001 using an Aerosol Mass Spectrometer - Part II: Chemically Speciated Mass Distributions Frank Drewnick, John T. Jayne, Manjula Canagaratna, Douglas R. Worsnop, Kenneth L. Demerjian Atmospheric Sciences Research Center, State University of New York, 251 Fuller Road, Albany, NY 12203, USA (F.D., K.L.D.) Center for Aerosol and Cloud Chemistry, Aerodyne Research Inc, 45 Manning Road, Billerica, MA 01821­3976, USA (J.T.J., M.C., D.R.W.) (Submitted to Aerosol Science & Technology). Intercomparison and Evaluation of Four Semi-continuous PM-2.5 Sulfate Instruments

• F. Drewnick, J. J. Schwab, O. Hogrefe, S. Peters, L. Husain1, D. Diamond2, R. Weber2 and K.
• L. Demerjian

Atmospheric Sciences Research Center, University at Albany, State University of New York, 251 Fuller Road, Albany, NY

1NYS Department of Health, Wadsworth Center, Albany, NY 2School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA

(Submitted to Atmospheric Environment). Advances in Continuous Measurement Methods for PM-2.5 Mass: Part 1. Laboratory Studies of a 30°C TEOM with Nafion Dryer and of a Self-correcting TEOM with Electrostatic Precipitator James J. Schwab, Jeffrey Ambs, Olga Hogrefe, and Kenneth L. Demerjian Atmospheric Sciences Research Center, University at Albany, State University of New York; and Rupprecht and Patashnick Company, Inc. (Submitted to Air Waste Management).

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Publications Submitted (continued)

Advances in Measurement Methods for PM-2.5 Mass: Part 2. Field Evaluations of the 30°C TEOM Monitor with Nafion Dryer in Rural and Urban Locations, and Comparisons with 50°C TEOM Monitor and FRM 24 Hour Integrated Filters James J. Schwab, Jeffrey Ambs, John Spicer, Dirk Felton, and Kenneth L. Demerjian Atmospheric Sciences Research Center, University at Albany, State University of New York; NYSDEC; and Rupprecht and Patashnick Company, Inc. (Submitted to Journal of the Air & Waste Management Association). Mobile Particulate Emission Studies of in-use New York City Vehicles Manjula R. Canagaratna1, John T. Jayne1, Asher Ghertner2, Scott Herndon1, Joanne Shorter 1, Mark Zahniser1, Quan Shi1, Jose Jimenez 3, Thomas Lanni4, Frank Drewnick5, Kenneth L. Demerjian5, Charles E. Kolb1, Douglas R. Worsnop1

1Aerodyne Research, Inc. Billerica, MA 2 University of California, Berkeley, CA 3 University of Colorado, Boulder, CO 4 Department of Environmental Conservation, New York, NY 5 University of Albany, Albany, NY

(Submitted to Aerosol Science & Technology). Intercomparison and Performance Evaluation of Semi-Continuous PM-2.5 Nitrate Instruments during the PMTACS-NY Summer 2001 Campaign in New York City

‡ ‡

• O. Hogrefe, F. Drewnick, J.J. Schwab, S. Peters, D. Diamond , R. Weber and K. L. Demerjian

Atmospheric Sciences Research Center, University at Albany, State University of New York, 251

‡

Fuller Road, Albany, NY 12203; School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332 (Submitted to Atmospheric Environment). OH and HO2 Chemistry in the Urban Atmosphere of New York City Xinrong Ren1*, Hartwig Harder1,2, Monica Martinez1,2, Robert L. Lesher1, Angelique Oliger1, James B. Simpas1, William H. Brune1, James J. Schwab3, Kenneth L. Demerjian3, Yi He4, Xianliang Zhou4,5, and Honglian Gao5

1Department of Meteorology, Pennsylvania State University, University Park, PA 16802, USA 2Now at Max­Planck­Institut für Chemie, D­55116 Mainz, Germany 3Atmospheric Sciences Research Center, University at Albany, State University of New York, Albany,

NY 12203, USA

4Department of Environmental Health and Toxicology, University at Albany, State University of New

York, Albany, NY 12222, USA

5Wadsworth Center, New York State Department of Health, Albany, NY 12201, USA

(Submitted to Atmospheric Environment).

SO2 vs NOx as a Function of CO

so2.ppb

co.ppb: 109.2 to 314.2 co.ppb: 314.2 to 467.6 co.ppb: 467.9 to 1,938.9

50 100 150 200 250 nox.ppb 30 10 30 10 30 10