Speciation of Organics in PM2.5 for the New York City Area

Transcription

1 Speciation of Organics in PM2.5 for the New York City Area Contributors Monica Mazurek, Min Li Rutgers University Steve McDow, NERL U.S. EPA John Graham, NESCAUM Dirk Felton, NYDEC Tom McKenna, Charlie Pietarinen, NJDEP Al Leston, Steve Bailey, CT DEP Presented at MARAMA/NESCAUM Science Meeting October 18-20,2004, Atlantic City, NJ Support Northeast States for Coordinated Air Use Management (NESCAUM) New York State Energy & Research Development Authority (NYSERDA) National Science Foundation, Atmospheric Chemistry

2 There are about 65 million people in the United States that live with annual average PM 2.5 levels above 15 µg/m 3. Average PM 2.5 concentrations from FRM monitors in the EPA AIRS database 7/98 through 7/00. NARSTO Assessment 2003

3 Eastern U.S. Fine Mass Rural Urban NARSTO Assessment, 2003

4 Speciation of Organics for Source Apportionment of PM-2.5 (SOAP) Project Objectives Ambient concentrations molecular markers Mass ratios organic markers to ambient EC, OC Sources of fine carbonaceous particles Toll Plaza 13, NJ Turnpike, Elizabeth, NJ

5 Detection Limits & Contaminant Minimization Tisch 2-Channel Sampler Quartz fiber filter collection substrate YEAR 1 Sampling, transport, sample handling, and analytical procedures for ppb-level organics

6 PM-2.5 Collection SOAP network field program Queen s College NY Supersite Elizabeth, NJ Chester, NJ Westport, CT YEAR 2 Completed full annual cycle May using Speciation Trends Network Schedule 400 successful ambient filters

7 SOAP Fine Particle Composites Identical days, 6-10 filters per composite Early summer 02 Eliz, Qns, Chs Summer 02 Eliz, Qns, Wpt, Chs Early fall, 02 Eliz, Qns, Wpt, Chs Fall, 02 Eliz, Qns, Wpt, Chs Fall, 02 precision Eliz, Qns, Wpt, Chs(2) Early winter, Eliz, Qns, Wpt, Chs Winter, 03 Eliz, Qns, Wpt, Chs Early spring, 03 Eliz, Qns, Wpt, Chs Spring, 03 Eliz, Qns, Wpt, Chs Late spring, 03 Eliz, Qns, Wpt, Chs

8 SOAP Fine Particle EC, OC Archive 25% LCMS Polar 25% Filters GCMS markers 50% Color range chart

9 Carbon Chemical Mass Balance Accounts for various forms of organic carbon Multiple analytical measurements Monitor variations in fine aerosol composition from bulk C to molecular organic C West Los Angeles (Rogge et al., 1993)

10 Filter Composite Extraction Seasonal Composites Extracted by Groups 6-10 filters per composite QA/QC Analytical, trip and field blanks Sensitivity and procedural tests, stds and test ambient

11 Filter Composite Extraction & Derivatization 4 hrs Soxhlet extraction 250 ml (1:1) acetone:ch 2 Cl 2 Extract concentration Kuderna-Danish appar. (5ml) N 2 gas (1ml) Extract Split (1:1) Neutral organics Acid+Neutral organics Diazomethane synthesis Conversion Acid+Neutral to methyl esthers, methoxy ethers

12 PM-2.5 Complex Mixture Analysis Molecular Marker Analysis GCMS ion trap analysis neutral and derivatized fractions YEAR 3 Molecular marker identification & quantitation Data interpretation

13 SOAP Molecular Markers Alkanes n-pentacosane n-hexacosane n-heptacosane n-octacosane n-nonacosane n-triacontane n-hentriacontane n-dotriacontane anteiso-triacontane iso-hentriacontane anteisohentriacontane iso-dotriacontane anteisodotriacontane iso-tritriacontane phytane pristane PAHs benzo[b]fluoranthene benzo[k]fluoranthene benzo[e]pyrene indeno[1,2,3-cd]pyrene indeno[1,2,3- cd]fluoranthene retene coronene Acids 21 n-alkanoic acids (with C 10 to C 30 ) 10 aliphatic dicarboxylic acids (C 3 to C 10 ) 1 aromatic polycarboxylic acid cis-9-n-octadecenoic acid Other 9hopanes nonanal levoglucosan galactosan mannosan cholesterol 7H-benz[de]anthracen-7-one benz[a]anthracene-7,12-dione Authentic standards for 63 marker cmpds measured in SOAP ambient composites

14 N-Alkane Carbon Number and Source Provenance Surface waxes from vegetation vs. gasoline, diesel fuels Distribution of hydrocarbons versus Carbon Number Mazurek and Simoneit, 1984

15 Carbon Preference Index (CPI) and Source Provenance N-Alkanes & N-Alkanones Carbon Preference Index = odd homologs even homologs N-Fatty Acids & N-Alkanols Carbon Preference Index = even homologs odd homologs

16 Carbon Preference Index (CPI) & Carbon Number Distribution CPI > 3 Significant contribution of recent biological material CPI ~ 1 Significant contribution degraded material and fossil fuel compounds Homolog Range and Carbon Number Maximum Source Range CMax Bacterial, microbial C15-C19 C16, C18 Petroleum hydrocarbons C12-C35 C23-C24 Plant waxes C22-C36 C27, C29 Mazurek and Simoneit, 1984

17 NYC Area Ambient Concentrations Alkanes n-pentacosane n-hexacosane n-heptacosane n-octacosane n-nonacosane n-triacontane n-hentriacontane n-dotriacontane anteiso-triacontane iso-hentriacontane anteisohentriacontane iso-dotriacontane anteisodotriacontane iso-tritriacontane phytane pristane ng/m N-Alkanes (C25-C32) 2.3 n-alkanes (C25-C32) Carbon Preference Index = odd homologs even homologs Qns 1 Qns 2 Elz 1 Elz 2 Chs 1 Chs 2 Wpt 1 Wpt 2 Composite 1: Winter Dec02, Jan03, Feb03 (6 filters) Composite 2: Spring Mar03, Apr03 (10 filters) 2.0

18 NYC Area Molecular Markers Acids 21 n-alkanoic acids (with C 10 to C 30 ) CPI noted above bar N-Alkanoic Acids (C10-C30) and Diacids (C3-C9) n-alkanoic acids (C10-C30) and diacids (C3-C9) aliphatic dicarboxylic acids (C 3 to C 10 ) 1 aromatic polycarboxylic acid cis-9-n-octadecenoic acid ng/m Qns 1 Qns 2 Elz 1 Elz 2 Chs 1 Chs 2 Wpt 1 Wpt 2 Composite 1: Winter Dec02, Jan03, Feb03 (6 filters) Composite 2: Spring Mar03, Apr03 (10 filters)

19 NYC Area Vehicle Emission Markers in Fine Particle Samples Composite 1 Winter -- Dec 2002, Jan + Feb 2003 (6 filters) Composite 2 Spring -- Mar + April 2003 (10 filters) ng/m Hopanes (C27-C32) Hopane detection limit > 0.01 ng/m3 Qns 1 Qns 2 Elz 1 Elz 2 Chs 1 Chs 2 Wpt 1 Wpt 2

20 NYC Area PM-2.5 Organics (STN) SOAP Composite OC µg/m 3 Organics µg/m 3 EC µg/m 3 Hopanes/ Organics Ratio (10-3 ) Elz, summer Hopanes/EC Ratio (10-3 ) Elz, fall Elz, winter Elz, spring Qns, fall Qns, winter Qns, spring Wpt, winter Wpt, spring Chs, spring

21 Estimating Source Contribution Total C (EC+OC) : Organic Matter (1.4 X OC) : Elutable Organic Matter : Molecular Tracer Mass emission ratios hopane concentration ng/m 3 OC concentration µg/ m 3 = ratio of source emission rates Rogge et al., 1993 vehicle exhaust = 2.7X10-3 Relative Source Contribution to Modeled OC Compounds Ambient Concentrations Diesel vehicles = 60% Gasoline Vehicles = 30% Paved road dust = 10% Schauer et al., 1996

22 Comparison to Los Angeles Area Total C (EC+OC) : Organic Matter (1.4 X OC) : Elutable Organic Matter : Molecular Tracer Metropolitan Los Angeles 1982, Chemical Mass Balance Schauer et al., 1996 Site Organics µg/m 3 Ratio Hopanes ng/m 3 to Organics µg/m 3 (10^-3) Organics from Diesel+ Gasoline Vehicles µg/m 3 (% Fine Particle Mass) Organics from All Vehicle (road dust, tire debris µg/m 3 (% Fine Particle Mass) Pasadena (24%) 3.13 (38%) Downtown LA (42%) 4.97 (54%) West LA (24%) 2.68 (37%) Rubidoux (14%) 2.40 (27%)

23 Comparison to Los Angeles Area 1982 Site Organics µg/m 3 Ratio Hopanes ng/m 3 to Organics µg/m 3 (10^-3) Organics from Diesel+ Gasoline Vehicles µg/m 3 (% Fine Particle Mass) Organics from All Vehicle (road dust, tire debris µg/m 3 (% Fine Particle Mass) Pasadena (24%) 3.13 (38%) Downtown LA (42%) 4.97 (54%) West LA (24%) 2.68 (37%) Rubidoux (14%) 2.40 (27%) Elizabeth, NJ % est. max. 54% est. max. Queens, NY % est. max. 54% est. max. Westport, CT % est. max. 38% est. max. Chester, NJ % est. max. 27% est. max.

24 Preliminary Findings n-alkanes: winter> spring CPI spring,summer > winter increased input of biogenic sources n-alkanoic acids & diacids: ambient concentrations similar each site, composite diacids not only photochemical sources CPI>3 for n-alkanoic acids suggest biogenic origin DISCLAIMER: Although this work was reviewed by EPA and approved for publication, it may not necessarily reflect official Agency policy. Hopanes: winter maxima Elz>Qns>>Wpt>Chs estimate maximum organics from all motor vehicle sources 27% to 54%

25 Air Quality Trends Control of gas phase pollutants (NO X, SO X, O 3 ) and PM has improved urban atmospheres

26 Thank you

27 End of Presentation