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

There are about 65 million people in the United States that live with annual average PM 2.5 levels above 15 g/m3.

Average PM2.5 concentrations from FRM monitors in the EPA AIRS database 7/98 through 7/00. NARSTO Assessment 2003

Eastern U.S. Fine Mass

Rural Urban

NARSTO Assessment, 2003

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

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

PM-2.5 Collection
SOAP network field program
Queens College NY Supersite Elizabeth, NJ Chester, NJ Westport, CT

YEAR 2
Completed full annual cycle May 2002-2003 using Speciation Trends Network Schedule

400 successful ambient filters

Identical days, 6-10 Early summer 02 Summer 02 Early fall, 02 Fall, 02 Fall, 02 precision Early winter, 02-03 Winter, 03 Early spring, 03 Spring, 03 Late spring, 03

SOAP Fine Particle Composites

filters per composite Eliz, Qns, Chs Eliz, Qns, Wpt, Chs Eliz, Qns, Wpt, Chs Eliz, Qns, Wpt, Chs Eliz, Qns, Wpt, Chs(2) Eliz, Qns, Wpt, Chs Eliz, Qns, Wpt, Chs Eliz, Qns, Wpt, Chs Eliz, Qns, Wpt, Chs Eliz, Qns, Wpt, Chs

SOAP Fine Particle Filters

Color range chart

EC, OC Archive 25% LCMS Polar 25%

GCMS markers 50%

Carbon Chemical Mass Balance

Accounts for
various forms of organic carbon analytical measurements variations in fine aerosol composition from bulk C to molecular organic C

West Los Angeles (Rogge et al., 1993)

Multiple Monitor

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

Filter Composite Extraction & Derivatization

4 hrs Soxhlet extraction 250 ml (1:1) acetone:CH2Cl2 Extract concentration Kuderna-Danish appar. (5ml) N2 gas (1ml) Extract Split (1:1) Neutral organics Acid+Neutral organics Diazomethane synthesis Conversion Acid+Neutral to methyl esthers, methoxy ethers

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

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[1,2,3cd]fluoranthene retene coronene Acids 21 n-alkanoic acids (with C10 to C30) 10 aliphatic dicarboxylic acids (C3 to C10) 1 aromatic polycarboxylic acid cis-9-n-octadecenoic acid Other 9 hopanes 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

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

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

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
Bacterial, microbial Petroleum hydrocarbons Plant waxes Mazurek and Simoneit, 1984

Range
C15-C19 C12-C35 C22-C36

CMax
C16, C18 C23-C24 C27, C29

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

N-Alkanes (C25-C32)
12 10 8
ng/m3

n-Alkanes (C25-C32) Carbon Preference Index = odd homologs even homologs

1.5 1.7

6 4 2 0 Qns 1 Qns 2 Elz 1

2.3

2.6

1.2 1.9 2.7 2.0

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)

NYC Area Molecular Markers

Acids 21 n-alkanoic acids (with C10 to C30) CPI noted above bar
120 100 80
ng/m3

N-Alkanoic Acids (C10-C30) and Diacids (C3-C9)

n-Alkanoic acids (C10-C30) and diacids (C3-C9)
21.5

10 aliphatic dicarboxylic acids (C3 to C10) 1 aromatic polycarboxylic acid cis-9-n-octadecenoic acid

60 40 20 0

50.1 14.4

16.0 12.6 16.9 18.0 18.0

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)

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/m3

Hopanes (C27-C32)
3 2 2 1 1 0 Qns 1 Qns 2 Elz 1 Elz 2 Chs 1 Chs 2 Wpt 1 Wpt 2
Hopane detection limit > 0.01 ng/m3

NYC Area PM-2.5 Organics (STN)

SOAP Composite OC g/m3 Organics g/m3
9.17 5.91-6.37 9.60-10.20 7.52-8.41 3.02 2.86-6.00 4.48-4.84 5.27-5.98 4.21-4.48 3.56-4.62

EC g/m3
1.65 1.59-1.72 1.69-1.77 1.39-1.94 0.60 0.46-1.16 0.82-0.89 0.74-0.21 0.70-0.80 0.41-0.47

Hopanes/ Organics Ratio (10-3)

Hopanes/EC Ratio (10-3)

Elz, summer 6.55 Elz, fall Elz, winter Elz, spring Qns, fall Qns, winter Qns, spring Wpt, winter Wpt, spring Chs, spring 4.22-4.55 6.86-7.28 5.37-6.01 2.16 2.04-4.28 3.20-3.46 3.77-4.27 3.01-3.20 2.54-3.30

0.14 0.18-0.19 0.24-0.37 0.14-0.39 0.30 0.29-0.32 0.15-0.32 0.03-0.22 0.08-0.14 0.03-0.04

0.80 0.62-0.77 1.38-2.09 0.77-1.74 1.54 1.64-1.79 0.83-1.90 0.20-1.11 0.44-0.85 0.29

Estimating Source Contribution

Total C (EC+OC) : Organic Matter (1.4 X OC) : Elutable Organic Matter : Molecular Tracer

Mass emission ratios hopane concentration ng/m3 = ratio of source emission rates

OC concentration g/ m3 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

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 g/m3 Ratio Hopanes ng/m3 to Organics g/m3 (10^-3) 0.46-0.89 0.43-0.83 0.53-1.04 0.60-1.17 Organics from Diesel+ Gasoline Vehicles g/m3 (% Fine Particle Mass) 2.44 (24%) 4.28 (42%) 2.08 (24%) 1.51 (14%) Organics from All Vehicle (road dust, tire debris g/m3 (% Fine Particle Mass) 3.13 (38%) 4.97 (54%) 2.68 (37%) 2.40 (27%)

Pasadena Downtown LA West LA Rubidoux

8.14 8.72 7.00 6.24

Comparison to Los Angeles Area 1982

Site Organics g/m3 Ratio Hopanes ng/m3 to Organics g/m3 (10^-3) Organics from Diesel+ Gasoline Vehicles g/m3 (% Fine Particle Mass) Organics from All Vehicle (road dust, tire debris g/m3 (% Fine Particle Mass) 3.13 (38%) 4.97 (54%) 2.68 (37%) 2.40 (27%)

Pasadena Downtown LA West LA Rubidoux Elizabeth, NJ Queens, NY Westport, CT Chester, NJ

8.14 8.72 7.00 6.24 5.91-10.20 2.16-4.28 4.21-5.98 3.56-4.62

0.46-0.89 0.43-0.83 0.53-1.04 0.60-1.17 0.14-0.39 0.15-0.29 0.03-0.22 0.03-0.04

2.44 (24%) 4.28 (42%) 2.08 (24%) 1.51 (14%)

42% est. max. 42% est. max. 24% est. max. 14% est. max.

54% est. max. 54% est. max. 38% est. max. 27% est. max.

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 Hopanes: winter maxima Elz>Qns>>Wpt>Chs estimate maximum organics from all motor vehicle sources 27% to 54%

DISCLAIMER: Although this work was reviewed by EPA and approved for publication, it may not necessarily reflect official Agency policy.

Air Quality Trends

Control of gas phase pollutants (NOX, SOX, O3) and PM has improved urban atmospheres

Thank you

End of Presentation