Identification of Identification of Transportation Transportation

Contributions to Urban Contributions to Urban PMPM

LevelsLevelsAQRB Mid-Term Review 2004

J.R. Brook + many contributors

MSC

OverviewOverview• PERD 'POL' on transportation and

particulate matter.– Multiple Gov't partners

– Emphasis on organic fraction

• Continuing analysis of Toronto and Vancouver 'TSRI' daily time series of PM2.5 speciation.

– Receptor modelling

• Organic speciation of PM2.5

Measurement of OC & EC

0

100

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700

800

900

1000

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0

Time (minutes)

Tem

pe

ratu

re (

C)

-50

150

350

550

750

950

FID

sig

na

l (C

H4

)

laser T CH4

OC1

OC2OC3

ECOC4PC

Thermal-Optical Transmission Analysis (TOT)

OC & EC Measurement Uncertainties

• High OC blanks (7-15 g per filter)• Deposit non-uniformity (~10% variability)• Uncertainty in pyrolysis correction based upon

BC absorbance (laser)• SVOC

– Positive and negative artifacts

• Enhanced charring due to artifacts and blank OC

• EC biased low?

• Conversion from ‘OC’ to ‘OM’

Toronto

Vancouver0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

2/14/00 5/24/00 9/1/00 12/10/00 3/20/01 6/28/01 10/6/01 1/14/02

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.00

0.02

0.04

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0.08

0.10

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0.14

2/14/00 5/24/00 9/1/00 12/10/00 3/20/01 6/28/01 10/6/01 1/14/02

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Oxa

lic

(g

m-3)

Oth

er a

cid

s (

g m

-3)

MalonicMalicSuccinicAzelaicOxalic

C WW C

0.0

2.0

4.0

6.0

8.0

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12.0

2/14/00 5/24/00 9/1/00 12/10/00 3/20/01 6/28/01 10/6/01 1/14/02

0.0

0.5

1.0

1.5

2.0

2.5

0.0

2.0

4.0

6.0

8.0

10.0

12.0

2/14/00 5/24/00 9/1/00 12/10/00 3/20/01 6/28/01 10/6/01 1/14/02

0.0

0.5

1.0

1.5

2.0

2.5

NO

(x1

00 p

pb

)

EC

(g

C m

-3)

O3 (

x10p

pb

)

O

C1

-3 O

C4

(

gC

m-3)

OC1-3OC4

O3

BCNO

C WW C

Time series of LMW acids & OC1-3, OC4, BC, NO and O3

PMF Estimates of PM2.5 Sources - Toronto

1.2 1.12.1

23

13

35

21

3.3 2.31.36

2.08

17

50

13

2.2 1.61.3

15

810

26

36

0

10

20

30

40

50

60

Secondary

Coal

Ammonium

Nitrate

Vehicle /

Road dust

Vehicle /

NaCl

Organic

Acids

PMprimary-1 Smelter PMprimary-2

Mas

s %

Summer Winter Annual

Coal Combustion Ammonium Nitrate Motor Vehicles

Sources of Organic Carbon - PMF

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

OC1 OC2 OC3 OC4 EC

PM primary-2

smelter

PM primary-1

LMW acid

Road salt/vehicle

Vehicle/road dust

Amm. Nitrate

Sec. Coal

Comparison of 2 Multi-Variate Methods

1.9%

2.2% 0.6%

3.7%

13.1%

8.0%

36.2%

18.2%

16.1%

2.2%1.4%

8.2%

10.1%

14.4%

1.3%

36.5%

26.0%

PMF UNMIX

Temporal Variation in PMF Sources

•For the 3 UNMIX motor vehicle related sources, day-of-week pattern is strongest for Diesel, weakest for Gas & intermediate for Road Dust.

•Day of week means are similar between the 2 PMF and 3 UNMIX motor vehicle related sources.

Vancouver PMF Source Characteristics

1.E-61.E-51.E-41.E-31.E-21.E-1

1.E+01.E+11.E+2

0.0

0.2

0.4

0.6

0.8

1.0

Mass EVSOA+Sulphate

1.E-51.E-41.E-31.E-21.E-1

1.E+01.E+11.E+21.E+3

0.0

0.2

0.4

0.6

0.8

1.0

Mass EVMotor Vehicles

1.E-51.E-41.E-31.E-21.E-1

1.E+01.E+11.E+2

0.0

0.2

0.4

0.6

0.8

1.0

Mass EVNaCl

1.E-6

1.E-4

1.E-2

1.E+0

1.E+2

0.0

0.2

0.4

0.6

0.8

1.0

Mass EVNaNO3

PMF Estimate of PM2.5 Sources - Vancouver

0

10

20

30

40

50

60C

rus

tal/

Al

Ni/

Cr

Pb

/As

Ba

/FO

RM

V/N

i

Na

NO

3

Na

Cl

NH

4N

O3

NH

4S

O4

/ac

id

Ve

hic

les

Summer Winter Total

% C

ontr

ibu

tion

to P

M2

.5

R2 = 0.23

0

2

4

6

8

10

12

0 2 4 6 8

R2 = 0.40

0

2

4

6

8

10

12

0 2 4 6 8 10 12

R2 = 0.78

0

2

4

6

8

10

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14

0 5 10 15 20

R2 = 0.04

0

2

4

6

8

10

12

0 2 4 6 8

OC

1-3

(gC

m-3)

MV-PMF (g m-3) SOA-PMF (g m-3)

Van

couv

erT

oron

to

Relationship between OC and its two important sources

GOATS ConcentrationsGOATS Concentrations

Yonge Downsview Egbert

WD WE Holiday WD WE Holiday WD WE

PM2.5 (ug/m3) 14.94 17.09 41.39 9.42 12.84 30.60 6.82 9.32

OC (ug/m3) 5.33 6.45 5.05 5.89 5.58 9.30 4.45 7.53

EC (ug/m3) 1.42 0.64 0.88 0.37 0.32 1.02 0.05 0.18

Total Biomarkers 1.98 1.00 1.13 0.78 0.54 0.90 0.03 0.00

Total Alkanes 19.64 13.29 14.09 16.91 9.16 17.28 7.93 8.27

Total cyclo-alkanes 1.06 0.20 0.37 0.16 0.14 0.27 0.00 0.00

Total PAH 2.53 1.37 1.46 0.60 0.76 1.37 0.13 0.35

Total fatty acids 460.38 680.50 1052.55 461.84 561.19 744.32 313.43 353.56

Levoglucosan 186.85 1129.87 303.56 417.41 1596.93 2175.20 91.45 64.00

Cholesterol 0.00 3.48 28.48 0.00 0.00 18.40 0.00 7.27

Concentrations are in ng m-3 unless noted

PM2.5 “semi-hivol” sampling in spring-summer 2000Yonge – eastbound 401 on ramp from northbound Yonge St.Downsview – roof of MSCEgbert – Centre for Atmospheric Research Experiments

GOATS %OC ExplainedGOATS %OC ExplainedC

on

cen

trat

ion

(n

g m

-3)

0.00

0.01

0.10

1.00

10.00

100.00

1000.00

10000.00

100000.00

Yon

ge -

WD

Yon

ge -

WE

Yon

ge -

Hol

Dow

nsvi

ew -

WD

Dow

nsvi

ew -

WE

Dow

nsvi

ew -

Hol

Egb

ert -

WD

Egb

ert -

WE

PM2.5

OC

Total fattyacidsLevoglucosan

Total Alkanes

Cholesterol

Total PAH

Total cyclo-alkanesTotalBiomarkers

13%13% 28%28% 28%28% 15%15% 39%39% 32%32% 9%9% 6%6%

•Humic-like substances (‘HULIS’) is one of the more exciting areas of OC-speciation research at present time.

*OC4 and the ‘UCM or hump’ are hypothesized to be related to HULIS*polymerized carbonyl compounds could be part of HULIS

•Importance of primary biologicals is also becoming increasingly recognized.

*4-11% of PM2.5 at Yonge was found to be associated with fungal spores.

Future ActivitiesFuture Activities• Renewal of PERD-POL is pending

• CRUISER has been proposed to take a central role in the ambient characterization component of this new POL

• A new joint proposal on black carbon and climate effects has been submitted to the Climate Change Technology & Innovation Transportation R&D program

• Ongoing comparison of independent receptor model results using same data and similar and different methods (MSC, UofT, P&Y)

• Past organic speciation results continue to be analyzed• Progress is slow due to lack of time

• Two years of monthly average concentrations (a composite of daily samples from downtown Toronto TSRI site) of a range of organic species is nearing completion.

• Analysis of levoglucosan, fatty acids, alkanes and biomarkers to begin soon

• Will provide our first look at the seasonal cycle in Toronto

• Methods are being developed for TD-CGMS• No solvents or extraction

• Can utilize low volume samples

• First step is to focus on PAHs and alkanes for health/exposure studies

Sources of Selected ConstituentsUNMIX Model