Page 1
SupportNortheast States for Coordinated Air Use
Management (NESCAUM)
New York State Energy & Research Development Authority (NYSERDA)
National Science Foundation, Atmospheric Chemistry
Speciation of Organics in PM2.5 for the
New York City Area
ContributorsMonica Mazurek, Min Li
Rutgers University
Steve McDow, NERL U.S. EPAJohn Graham, NESCAUMDirk Felton, NYDECTom McKenna, Charlie
Pietarinen, NJDEPAl Leston, Steve Bailey, CT DEP
Presented atMARAMA/NESCAUM Science MeetingOctober 18-20,2004, Atlantic City, NJ
Page 2
There are about 65 million people in the United States that live with annual average PM 2.5 levels above 15 µg/m3.
Average PM2.5 concentrations from FRM monitors in the EPA AIRS database 7/98 through 7/00. NARSTO Assessment 2003
Page 3
Eastern U.S. Fine MassRural Urban
NARSTO Assessment, 2003
Page 4
Sources of fine carbonaceous particles
Mass ratios organic markers to ambient EC, OC
Toll Plaza 13, NJ Turnpike, Elizabeth, NJ
Speciation of Organics for Source Apportionment of PM-2.5 (SOAP) Project
ObjectivesAmbient concentrationsmolecular markers
Page 5
Detection Limits & Contaminant Minimization
Tisch 2-Channel Sampler
Quartz fiber filter collection substrate
YEAR 1Sampling, transport, sample handling, and analytical procedures for ppb-level organics
Page 6
PM-2.5 Collection
•
•
•
•SOAP network field programQueen’s College NY
SupersiteElizabeth, NJChester, NJWestport, CT
YEAR 2Completed full annual cycle May 2002-2003 using Speciation Trends Network Schedule
400 successful ambient filters
Page 7
SOAP Fine Particle CompositesIdentical days, 6-10 filters per composite
Early summer ‘02 Eliz, Qns, ChsSummer ’02 Eliz, Qns, Wpt, ChsEarly fall, ’02 Eliz, Qns, Wpt, ChsFall, ’02 Eliz, Qns, Wpt, ChsFall, ’02 precision Eliz, Qns, Wpt, Chs(2)Early winter, ’02-’03 Eliz, Qns, Wpt, ChsWinter, ’03 Eliz, Qns, Wpt, ChsEarly spring, ’03 Eliz, Qns, Wpt, ChsSpring, ’03 Eliz, Qns, Wpt, ChsLate spring, ‘03 Eliz, Qns, Wpt, Chs
Page 8
EC, OC Archive
LCMS Polar
25%
25%
50%
GCMS markers
SOAP Fine Particle Filters
Color range chart
Page 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)
Page 10
Seasonal Composites Extracted by Groups6-10 filters per compositeQA/QC
Analytical, trip and field blanks
Sensitivity and procedural tests, stds and test ambient
Filter Composite Extraction
Page 11
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
Page 12
Molecular Marker Analysis
GCMS ion trap analysis neutral and derivatized fractions
YEAR 3Molecular marker identification & quantitation
Data interpretation
PM-2.5 Complex Mixture Analysis
Page 13
SOAP Molecular MarkersAlkanes
n-pentacosanen-hexacosanen-heptacosanen-octacosanen-nonacosanen-triacontanen-hentriacontanen-dotriacontaneanteiso-triacontaneiso-hentriacontaneanteiso-hentriacontaneiso-dotriacontaneanteiso-dotriacontaneiso-tritriacontanephytanepristane
PAHsbenzo[b]fluoranthenebenzo[k]fluoranthenebenzo[e]pyreneindeno[1,2,3-cd]pyreneindeno[1,2,3-cd]fluorantheneretenecoronene
Other9 hopanes nonanallevoglucosangalactosanmannosancholesterol7H-benz[de]anthracen-7-onebenz[a]anthracene-7,12-dione
Acids21 n-alkanoic acids(with C10 to C30)10 aliphatic dicarboxylicacids(C3 to C10)1 aromatic polycarboxylicacid cis-9-n-octadecenoic acid
Authentic standards for 63 marker cmpdsmeasured in SOAP ambient composites
Page 14
N-Alkane Carbon Number and Source Provenance
Distribution of hydrocarbons versus Carbon Number
Mazurek and Simoneit, 1984
Surface waxes from vegetation vs. gasoline, diesel fuels
Page 15
Carbon Preference Index (CPI) and Source Provenance
Carbon Preference Index = ∑odd homologs∑even homologs
Carbon Preference Index = ∑even homologs∑odd homologs
N-Alkanes & N-Alkanones N-Fatty Acids & N-Alkanols
Page 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 CMaxBacterial, microbial C15-C19 C16, C18
Petroleum hydrocarbons C12-C35 C23-C24
Plant waxes C22-C36 C27, C29
Mazurek and Simoneit, 1984
Page 17
NYC Area Ambient Concentrations
n-Alkanes (C25-C32)
0
2
4
6
8
10
12
Qns 1 Qns 2 Elz 1 Elz 2 Chs 1 Chs 2 Wpt 1 Wpt 2
ng
/m3
Composite 1: Winter Dec02, Jan03, Feb03 (6 filters)
Composite 2: Spring Mar03, Apr03 (10 filters)
1.5
2.3
1.7
2.6 1.2
2.71.9 2.0
N-Alkanes (C25-C32)
Carbon Preference Index = ∑odd homologs∑even homologs
Alkanesn-pentacosanen-hexacosanen-heptacosanen-octacosanen-nonacosanen-triacontanen-hentriacontanen-dotriacontaneanteiso-triacontaneiso-hentriacontaneanteiso-hentriacontaneiso-dotriacontaneanteiso-dotriacontaneiso-tritriacontanephytanepristane
Page 18
NYC Area Molecular Markers
n-Alkanoic acids (C10-C30) and diacids (C3-C9)
0
20
40
60
80
100
120
Qns 1 Qns 2 Elz 1 Elz 2 Chs 1 Chs 2 Wpt 1 Wpt 2
ng
/m3
N-Alkanoic Acids (C10-C30) and Diacids (C3-C9)
Composite 1: Winter Dec02, Jan03, Feb03 (6 filters)
Composite 2: Spring Mar03, Apr03 (10 filters)
Acids
21 n-alkanoic acids
(with C10 to C30) CPI noted above bar
10 aliphaticdicarboxylic acids(C3 to C10)1 aromatic polycarboxylic acid cis-9-n-octadecenoicacid
21.5
16.0
12.616.9
18.018.0
50.114.4
Page 19
NYC Area Vehicle Emission Markers in Fine Particle Samples
Hopanes (C27-C32)
0
1
1
2
2
3
Qns 1 Qns 2 Elz 1 Elz 2 Chs 1 Chs 2 Wpt 1 Wpt 2
ng
/m3
Hopane detection limit > 0.01 ng/m3
Composite 1Winter --Dec 2002, Jan + Feb 2003 (6 filters)
Composite 2Spring --Mar + April 2003 (10 filters)
Page 20
NYC Area PM-2.5 Organics (STN)SOAP
CompositeOC
µg/m3Organics µg/m3
EC µg/m3
Hopanes/ Organics
Ratio (10-3)
Hopanes/EC Ratio (10-3)
Elz, summer 6.55 9.17 1.65 0.14 0.80
Elz, fall 4.22-4.55 5.91-6.37 1.59-1.72 0.18-0.19 0.62-0.77
Elz, winter 6.86-7.28 9.60-10.20 1.69-1.77 0.24-0.37 1.38-2.09
Elz, spring 5.37-6.01 7.52-8.41 1.39-1.94 0.14-0.39 0.77-1.74
Qns, fall 2.16 3.02 0.60 0.30 1.54
Qns, winter 2.04-4.28 2.86-6.00 0.46-1.16 0.29-0.32 1.64-1.79
Qns, spring 3.20-3.46 4.48-4.84 0.82-0.89 0.15-0.32 0.83-1.90
Wpt, winter 3.77-4.27 5.27-5.98 0.74-0.21 0.03-0.22 0.20-1.11
Wpt, spring 3.01-3.20 4.21-4.48 0.70-0.80 0.08-0.14 0.44-0.85
Chs, spring 2.54-3.30 3.56-4.62 0.41-0.47 0.03-0.04 0.29
Page 21
Estimating Source ContributionTotal C (EC+OC) : Organic Matter (1.4 X OC) :
Elutable Organic Matter : Molecular Tracer
Mass emission ratios
hopane concentration ng/m3
OC concentration µg/ m3
= ratio of source emission rates
Rogge et al., 1993 vehicle exhaust = 2.7X10-3
Relative Source Contribution to Modeled OC Compounds Ambient Concentrations
Schauer et al., 1996Diesel vehicles = 60% Gasoline Vehicles = 30%Paved road dust = 10%
Page 22
Comparison to Los Angeles AreaTotal C (EC+OC) : Organic Matter (1.4 X OC) :
Elutable Organic Matter : Molecular Tracer
Site Organics µg/m3
RatioHopanesng/m3 to Organics µg/m3
(10^-3)
Organics from Diesel+ Gasoline
Vehicles µg/m3
(% Fine Particle Mass)
Organics from All Vehicle (road dust, tire debris
µg/m3
(% Fine Particle Mass)
Pasadena 8.14 0.46-0.89 2.44 (24%) 3.13 (38%)
Downtown LA 8.72 0.43-0.83 4.28 (42%) 4.97 (54%)
West LA 7.00 0.53-1.04 2.08 (24%) 2.68 (37%)
Rubidoux 6.24 0.60-1.17 1.51 (14%) 2.40 (27%)
Metropolitan Los Angeles 1982, Chemical Mass Balance –Schauer et al., 1996
Page 23
Comparison to Los Angeles Area 1982Site Organics
µg/m3Ratio Hopanes
ng/m3 to Organics µg/m3
(10^-3)
Organics from Diesel+ Gasoline Vehicles µg/m3
(% Fine Particle Mass)
Organics from All Vehicle (road dust, tire debris µg/m3
(% Fine Particle Mass)
Pasadena 8.14 0.46-0.89 2.44 (24%) 3.13 (38%)
Downtown LA 8.72 0.43-0.83 4.28 (42%) 4.97 (54%)
West LA 7.00 0.53-1.04 2.08 (24%) 2.68 (37%)
Rubidoux 6.24 0.60-1.17 1.51 (14%) 2.40 (27%)
Elizabeth, NJ 5.91-10.20 0.14-0.39 42% est. max.42% est. max. 54% est. max.54% est. max.
Queens, NY 2.16-4.28 0.15-0.29 42% est. max.42% est. max. 54% est. max.54% est. max.
Westport, CT 4.21-5.98 0.03-0.22 24% est. max.24% est. max. 38% est. max.38% est. max.
Chester, NJ 3.56-4.62 0.03-0.04 14% est. max.14% est. max. 27% est. max.27% est. max.
Page 24
Preliminary Findingsn-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.
Page 25
Air Quality Trends
Control of gas phase pollutants (NOX, SOX, O3) and PM has improved urban atmospheres
Page 27
End of Presentation