Atmospheric Submicron Aerosol Organic Results from Aerosol Mass

Atmospheric Sub-micron Aerosol Organic: Results from Aerosol Mass Spectrometry Douglas R. Worsnop, John Jayne, Manjula Canagaratna, Tim Onasch, Hacene Boudries, Leah Williams Aerodyne Research, Inc. Jose Jimenez , Qi Zhang, Peter De. Carlo, Alex Huffman, Alice Delia University of Colorado Rami Alfarra, James Allan, Keith Bower, Hugh Coe UMIST Ann Middlebrook NOAA Jay Slowik, Paul Davidovits Boston College Frank Drewnick, Johannes Schneider MPI Mainz Silke Weimer, Ken Demerjian SUNY Albany European Monitoring and Evaluation Program (EMEP) Workshop on Particulate Matter (PM) Measurement United Nations Economic Commission for Europe New Orleans, Wednesday, April 21, 2004

Aerodyne Aerosol Mass Spectrometer (AMS) Particle Beam Generation Aerodynamic Sizing Particle Composition Quadrupole Mass Spectrometer Chopper Thermal Vaporization & Electron Impact Ionization TOF Region Aerodynamic Lens (2 Torr) Particle Inlet (1 atm) Turbo Pump 100% transmission (60 -600 nm), aerodynamic sizing, linear mass signal. Jayne et al. , Aerosol Science and Technology 33: 1 -2(49 -70), 2000. Jimenez et al. , Journal of Geophysical Research, 108(D 7), 8425, doi: 10. 1029 / 2001 JD 001213, 2003.

AMS: Size Resolved Chemical Composition of Sub-micron aerosol (PM 1) Non-refractory (NR) composition (thermal vaporization at 600 C) e. g. no black carbon (BC), dust or (typically) seasalt Electron Impact (EI) Mass Spectrometry – quantitative mass loading All NR components detected with little uncertainty direct calibration / chemically unbiased sample Mass spectrum of inorganics and organics easy to separate Analysis of organic matter (OM) – primary vs secondary hydrocarbon (lube oil) vs oxidized (HULIS) direct measure of OM/OC ratio Aerodynamic focusing and sizing collection efficiency 1 for aspherical particles; e. g. (NH 4)2 SO 4 measure CE with beam width probe – particle shape information aerodynamic (AMS) + mobility (SMPS) sizing particle mass, density, shape and fractal dimension + chemistry

Mass balance –TEOM, PILS, OC/EC Organic classification: primary vs oxidized OM/OC ratio Sizing – comparison with SMPS ( and Moudi) small, fractal organic vs mixed organic/sulfate accumulation dirunal and seasonal patterns compare to vehicle and dynometer emissions Future: To. F-AMS, higher sensitivity (aircraft time response) and single particle composition “cheaper, simpler” Q-AMS system hour time resolution size binning (<100 nm, 100 -200 nm, > 200 nm)

Real Time Chemical and Physical Composition of Aerosols Aerosol Sampling frequency - >10 Hz Real-time measurement. AMS Nitrate Sulphate Ammonium Organics Mass distribution Chemical composition Alkanes Aromatics Etc. .

EI Ionization: A + e- ----> A+ ----> ai+ Mass Loading A (MWA/IEA) Ion Signal ai Calibration Factor * (MWNO 3/IENO 3) EI Ionization Cross Sections

Typical ambient aerosol mass spectrum

MS Signatures for Aerosol Species Identification color coded to match spectra Group Molecule/Species Ion Fragments Mass Fragments Water H 2 O e- H 2 O+ , HO+ , O+ Ammonium NH 3 e- NH 3+, NH 2+, NH+ Nitrate HNO 3 e- HNO 3+, NO 2+, NO+ 18, 17, 16, 15 63, 46, 30 Sulfate H 2 SO 4 e- H 2 SO 4+, HSO 3+, SO 3+ 98, 81, 80 SO 2+, SO+ Organic (Oxygenated) Organic (hydrocarbon) C n Hm Oy C n Hm ee- H 2 O+, CO 2+ H 3 C 2 O+, HCO 2+, Cn’Hm+ Cn’Hm’+ 64, 48 18, 28, 44 43, 45, . . . 27, 29, 41, 43, 55, 57, 69, 71. . . Standard electron impact ionization @ 70 e. V Easy to quantify: ca. NIST MS library Easy to separate inorganic and organic components Speciation of organic composition is challenging

Comparison of PMTACS’ 01 and PMTACS’ 04 Time Series, Diurnal Plots, and Data Diagnostics Silke Weimer+, Frank Drewnick‡, Doug Worsnop*, Ken Demerjian+ + Atmospheric Sciences Research Center, Albany/NY, ‡ MPI for Chemistry, Mainz; *Aerodyne Res. Inc. /Billerica/MA

Mass Balance AMS vs. TEOM Speciated Mass, Queens, NY The “Other” Category -PM 1 vs PM 2. 5 -elemental carbon -crustal oxides Drewnick et al, 2003 F. Drewnick, J. Schwab, K. Demerjian ASRC SUNY Albany

Comparison of FDMS and AMS, PMTACS 04 PRELIMINARY WINTER AMS/FDMS ~ 0. 7 for AMS Particle Collection Efficiency: CE = 0. 5 FDMS – Dirk Felton, NYSDEC

10 minute data in PMTACS 04 PRLIMINARY ESTIMATED Primary organic Oxidized organic Plumes of primary organic are clearly observed - due to vehicles driving by the site (frequency increased after college re-opened in last week of study) Weimer, Drewnick et al

Organic Mass Spectra Cn. Hm e----> Cn’Hm’+ 27, 29, 41, 43, 55, 57, 69, 71, . . . C 4 H 9+ e. Cn. Hm. Oy ----> H 2 O+ CO 2+ C 2 H 3 O+ 18 28 44 43 27, 29, 55, …. Following flash vaporization at ~600 C

Diurnal Cycles of OM Classes Weimer, Drewnick et al Summer 57 – primary marker Winter 44 – oxidized marker

Aerosol Size-Resolved Composition with the Aerodyne AMS in Pittsburgh Jose-Luis Jimenez*, Qi Zhang, Manjula Canagaratna, John Jayne, Doug Worsnop, Charles Stanier, Spyros Pandis Dept. Chemistry & CIRES University of Colorado at Boulder * EPA Supersite Meeting Feb. 26, 2004

Primary Organic Component in Pittsburgh Zhang, Jimenez et al. Diesel Vehicle Exhaust Jayne, Canagaratna et al.

Oxidized Organic Component in Pittsburgh Zhang, Jimenez et al. Fulvic Acid “HULIS” ? ? Rami Alfarra et al (UMIST)

Total Organics Quantitation vs. Sunset Labs OC Pittsburgh “Super Site” OM / OC ~ 1. 7 Total Organic = C (all organic ions) Qi Zhang, Jose Jimenez, CU

FUTURE IDEAS lower cost “Cheaper” AMS – smaller, no fast electronics, limited size binning approaching cost and operational equivalent of RGA or GCMS simple calibration system? cost equivalent to collection of individual continuous instruments add thermal denuder to evaluate semivolatile component Aerosol Collection (with aerodynamic lens) (Paul Ziemann) – in situ (EI) mass spectrometric analysis - separation via volatility aerosol collection (< 1 hour) [ Hacene Boudries ] for direct injection into speciation detectors e. g. GCMS, PTRMS

Acknowledgments Aerodyne Doug Worsnop John Jayne Manjula Canagaratna Hacene Boudries Tim Onasch Phil Mortimer Leah Williams Boston College Jay Slowik Paul Davidovits Arizona State Jonathan Allen Utah State Phil Silva Boulder Jose Jimenez (UC) Alice Delia, Darren Toohey Ann Middlebrook (NOAA) Qi Zhang, Peter Decarlo (UC) Alex Huffman, Katja Dzepina UMIST Hugh Coe Keith Bower Paul Williams James Allen Rami Alfarra Caltech John Seinfeld, Rick Flagan Roya Bahreini MPI Mainz Frank Drewnick Johannes Schneider Stephan Borrmann Joachim Curtius Environment Canada Shao Meng Li, Jeff Brook Kathy Hayden, Gang Lu, Richard Leaitch SUNY Albany Ken Demerjian JAPAN Wyoming Nobu Tagekawa (Tokyo) Peter Liu Yutake Kondo (Tokyo) Derek Montague Akinori Takami (NIES) PNNL / BNL Akio Shimono (Sanyu) Ken-ichi Akiyama (JARI) Carl Berkowitz, Pete Daum MIT Xuefeng Zhang Ken Smith TOFWERK Marc Gonin Katrin Fuhrer CEH (Edinburgh) Eiko Nemitz David Anderson KFA Juelich Thomas Mentel Andreas Wahner Support: NSF, ONR, Do. E EPA, NASA, NOAA, JARI Environment Canada