Aerosol Composition in Los Angeles During the 2010 CalNex Campaign Studied by High Resolution...

Aerosol Composition in Los Angeles During the 2010 CalNex Campaign Studied by High Resolution Aerosol Mass Spectrometry

CalNex Data Analysis Workshop, May 16th – 19th 2011, Sacramento

Patrick L. Hayes1,2, Amber M. Ortega1,3, Michael J. Cubison1,2, Weiwei Hu4, Darin W. Toohey3, James H. Flynn5, Barry L. Lefer5, Sergio Alvarez5, Bernhard Rappenglück5, James D. Allan6, John S. Holloway1,7, Jessica B.

Gilman1,7, William C. Kuster7, Joost A. de Gouw1,7, Paola Massoli8, Xiaolu Zhang9, Rodney J. Weber9, Ashley Corrigan10, Lynn M. Russell10, Jose L. Jimenez1,2

(1) CIRES, Boulder, USA; (2) Department of Chemistry and Biochemistry, University of Colorado, Boulder, USA; (3) Department of Atmospheric and Oceanic Science, University of Colorado, Boulder, USA; (4) College of Environmental Sciences and Engineering, Peking University, China; (5) Department of Earth and Atmospheric Sciences, University of Houston, USA; (6) National Centre for Atmospheric Science, The University of Manchester, UK; (7) NOAA, Boulder, USA; (8) Aerodyne Research Inc., Billerica, USA; (9) Georgia Institute of Technology, Atlanta, USA; (10) Scripps Institution of Oceanography, University of

California San Diego, La Jolla, USA.

20

15

10

5

0

Mas

s C

once

ntra

tion

(µg/

m3 )

5/21/2010 5/31/2010 6/10/2010Date and Time (PDT)

BC Org NO3

SO4

NH4

Chl

Chemical Composition of PM1 Aerosols for Pasadena

• Build up of organic aerosol concentrations over a period of several days. Residual organic aerosols and precursor species in the Pasadena area appear to undergo multiple days of aging.

0.76

6.8

3.8

2.7

2.2

0.11

Organic

Nitrate

Sulfate

AmmoniumBlack CarbonChloride

Chemical Composition of Non-Refractory PM1 Aerosols for Pasadena

Diurnal Average (6/3 – 6/9):

16

14

12

10

8

6

4

2

0

Mas

s C

once

ntra

tion

(g/

m3 )

24201612840Diurnal Hour (PDT)

x20

Org NO3 SO4 NH4 Chl

• Organic diurnal trend consistent with transport times from source-rich western basin and the expected timescale of secondary production.

• Nitrate diurnal trend influenced by dilution due to rising planetary boundary layer and evaporation of ammonium nitrate.

Positive Matrix Factorization (PMF): Time Series & Mass Spectra

50

5/16/2010 5/21/2010 5/26/2010 5/31/2010 6/5/2010 6/10/2010 6/15/2010

Date and Time (PDT)

100

100

Mas

s C

once

ntr

atio

n (µ

g m

-3)

420

2.5

0.0

(LV-OOA)

(SV-OOA)

(LOA)

(HOA-ND)

(HOA-D)

PMF Background: Ulbrich et al. Atmos. Chem. Phys. 2009, 9, 2891.

Diesel Hydrocarbon-like Organic Aerosol (HOA-D)

Non-Diesel Hydrocarbon-like Organic Aerosol (HOA-ND)

Semi-Volatile OxygenatedOrganic Aerosol (SV-OOA)

Low-Volatility Oxygenated Organic Aerosol (LV-OOA)

Local Organic Aerosol(LOA)


50

5/16/2010 5/21/2010 5/26/2010 5/31/2010 6/5/2010 6/10/2010 6/15/2010

Date and Time (PDT)

100

100

Mas

s C

once

ntr

atio

n (µ

g m

-3)

420

2.5

0.0

(LV-OOA)

(SV-OOA)

(LOA)

(HOA-ND)

(HOA-D)

PMF Background: Ulbrich et al. Atmos. Chem. Phys. 2009, 9, 2891.

0.10

0.00

10080604020m/z

0.2

0.0

8040

0x10

-3

0.10

0.00 Fra

ctio

n of

Sig

nal

8040

0x10

-3

OM:OC=2.2, O:C=0.80, H:C=1.2, N:C=0.012

OM:OC=1.4, O:C=0.21, H:C=1.6, N:C=0.004

OM:OC=1.6, O:C=0.38, H:C=1.4, N:C=0.004

OM:OC=1.3, O:C=0.14, H:C=1.6, N:C=0.010

OM:OC=1.6, O:C=0.31, H:C=1.7, N:C=0.052

Cx

CHCHO1

CHO1+

CHNCHO1NCHON1+

CSHOAir






0.10

0.00

10080604020m/z

0.2

0.0

8040

0x10

-3

0.10

0.00 Fra

ctio

n of

Sig

nal

8040

0x10

-3

OM:OC=2.2, O:C=0.80, H:C=1.2, N:C=0.012

OM:OC=1.4, O:C=0.21, H:C=1.6, N:C=0.004

OM:OC=1.6, O:C=0.38, H:C=1.4, N:C=0.004

OM:OC=1.3, O:C=0.14, H:C=1.6, N:C=0.010

OM:OC=1.6, O:C=0.31, H:C=1.7, N:C=0.052

Cx

CHCHO1

CHO1+

CHNCHO1NCHON1+

CSHOAir







6

4

2

0Mas

s C

once

ntra

tion

(µg

m-3

)


HOA-D HOA-ND LOA SVOOA LVOOA

Ox(O3 + NO2) vs OOA

• Slope of OOA vs. Ox plot is steeper for Pasadena in comparison to Riverside (SOAR-1). • The OOA vs. Ox slope is similar to that found in Mexico City for less aged aerosol (MILAGRO).

20

15

10

5

Tot

al O

OA

Mas

s C

once

ntra

tion

(µg

m-3

)

6/3/2010 6/9/2010

Date and Time (PDT)

100

80

60

40

Ox (ppbv)

Ox OOA

Reference for OOA vs. Ox plots:Herndon et al. Geophys. Res. Lett. 2008, 35, L15804.Wood et al. Atmos. Chem. Phys. 2010, 10, 8947.

20

15

10

5

0

Tot

al O

OA

Mas

s C

once

ntra

tion

(µg

m-3

)

120100806040200

Ox (ppbv)

Linear ODR FitSlope = 0.151

R2 = 0.78

12:00 AM

6:00 AM

12:00 PM

6:00 PM

12:00 AM

Tim

e o

f Da

y (PD

T)

Comparison of HOA Components with Combustion Emission Tracers

1000

800

600BC

(ng

m-3

)

12:00 AM 6:00 AM 12:00 PM 6:00 PM 12:00 AM

Diurnal Hour (PDT)

340

320

300

280

260

CO

(p

pbv,

NO

AA

)0.750.700.650.600.550.500.45T

olue

ne (

ppbv

)

2.5

2.0

1.5

1.0

0.5

0.0

Mas

s C

onc.

(µg

m-3

)0.32

0.30

0.28

0.26

0.24

0.22

Benzene (ppbv)

700

600

500

400

EC

(ng m-3)

340

320

300

280

260

CO

(ppbv, U

niv. Hou.)

Toluene (NOAA) Benzene (NOAA) CO (NOAA) CO (Univ. Hou.) BC (Manchester Aeth) EC (GA Tech.) HOA-D HOA-ND

Gasoline Dominated

Diesel Dominated

More-Diesel Influenced

Less-Diesel Influenced

Taken from: Zhang et al. Geophys. Res. Lett. 2007, 34, L13801

Positive Matrix Factorization (PMF): Time Series & Campaign Averages

33%

34%

17%

12%

5%

LV-OOA

SV-OOA

HOA-D

HOA-NDLOA

Evolution of Org/DCO

30

Taken From: Dzepina et al. Atmos. Chem. Phys. 2009, 9, 5681.

Mexico City:

Kleinman et al. (2008)de Gouw et al. (2008)Dzepina et al. (2009)

Evolution of Org/DCO

30

Taken From: Dzepina et al. Atmos. Chem. Phys. 2009, 9, 5681.

Mexico City:

Pasadena:For 6/2 -6/6

80

60

40

20

0Org

/C

O (

µg

m-3

ppm

v-1)

00:00 06:00 12:00 18:00 00:00Diurnal Hour (PDT)

Univ. of Hou. CONOAA CO

30

HOA

SOA from previous day?

Kleinman et al. (2008)de Gouw et al. (2008)Dzepina et al. (2009)

Organic Aerosol Elemental Composition from High Resolution AMS data

HR-ToF-AMS Elemental Analysis Background: Aiken et al. Anal. Chem. 2007, 79, 8350.

0.48

0.46

0.44

0.42

0.40

0.38

O:C


1.50

1.48

1.46

1.44

1.42

1.40

H:C

1.80

1.78

1.76

1.74

1.72

1.70

1.68

1.66

1.64

OM

:OC

O:C mean H:C mean OM:OC mean

The Van Krevelen Diagram, Pasadena vs. Riverside

Reference for Van Krevelen Diagrams:Heald et al. Geophys. Res. Lett. 2010, 37, L08803.

• A shallower slope significantly less than -1 for Pasadena could be due to a greater tendency for alcohol addition, or C-C bond breaking (fragmentation) reactions during aerosol aging. Alternatively, slope may be due to different mixing of primary and secondary organic aerosol components.

2.0

1.8

1.6

1.4

1.2

1.0

H:C

1.00.80.60.40.20.0

O:C

Avg. CalNex Avg. SOAR

R2 = 0.83

slope = -0.64 Linear ODR Fit (CalNex)

Pasadena, CA (CalNex)Riverside, CA (SOAR)

The Van Krevelen Diagram, Pasadena vs. Riverside

Reference for Van Krevelen Diagrams:Heald et al. Geophys. Res. Lett. 2010, 37, L08803.

• A shallower slope significantly less than -1 for Pasadena could be due to a greater tendency for alcohol addition, or C-C bond breaking (fragmentation) reactions during aerosol aging. Alternatively, slope may be due to different mixing of primary and secondary organic aerosol components.

2.0

1.8

1.6

1.4

1.2

1.0

H:C

1.00.80.60.40.20.0

O:C

HOA-D HOA-ND LOA SV-OOA LV-OOA Avg. CalNex Avg. SOAR

R2 = 0.83



Thermodenuder + AMS and Volatility Distributions

1.20.80.40.0M

ass

Con

c. (

µg

m-3

)

10

-9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3Log C*

Particle Phase Total

Total OA:

0.300.200.100.00M

ass

Con

c. (

µg

m-3

)

-9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3Log C*

1

100 Particle Phase Total

POA (using C4H9 as surrogate):

Method From: Faulhaber et al. Atmos. Meas. Tech. 2009, 2, 15.

1.0

0.8

0.6

0.4

0.2

0.0

Mas

s F

ract

ion

Rem

aini

ng

(MF

R)

250200150100500TD Temperature (

oC)

C4H9 (Riverside, SOAR) C4H9 (Pasadena, CalNex)

1.0

0.8

0.6

0.4

0.2

0.0

Mas

s F

ract

ion

Rem

aini

ng

(MF

R)

250200150100500TD Temperature (

oC)

OA (Riverside, SOAR) OA (Pasadena, CalNex)

Acknowledgements

Funding:

CalNex Pasadena Ground-Site Team&

CalNex Scientific Community

Back-Up

2.0

1.8

1.6

1.4

1.2

1.0

H:C

1.00.80.60.40.20.0

O:C

Pasadena HOA-D HOA-ND LOA SV-OOA LV-OOA Avg. CalNex Avg. SOAR

Riverside LOA LV-OOA SV-OOA

R2 = 0.83



HOA-D vs. Black Carbon, ‘HOA-D + HOA-ND’ vs. CO(g)

Slope = 1.25

Slope = 1.41

Mexico City

Slope = 5.71

Slope = 3.33

MeMexico City

6

5

4

3

2

1

0

HO

A-D

Mas

s C

onc.

(µ

g m

-3)

3.02.01.00.0

BC Mass Concentration (µg m-3

)

Linear ODR Fit

Slope = 1.31, R2=0.49

16

12

8

4

0

'HO

A-D

' + 'H

OA

-ND

' Con

c. (

µg

m-3

)

0.60.40.20.0CO (ppmv)

Linear FitSlope=10.2

R2=0.49

8

6

4

2

0

Tot

al L

V-O

OA

Mas

s C

onc.

(µ

g m

-3)

120100806040200

Ox (ppbv)

12:00 AM 12:00 AMTime of Day (PDT)

Linear ODR Fit, Slope=0.014, R2=0.16

20

15

10

5

0

Tot

al S

V-O

OA

Mas

s C

onc.

(µ

g m

-3)

120100806040200

Ox (ppbv)

Linear ODR FitSlope=0.137

R2=0.79

12:00 AM 12:00 PM 12:00 AMTime of Day (PDT)

Ox(O3 + NO2) vs SV-OOA, Back-Up

0.30

0.25

0.20

0.15

0.10

0.05

0.00

f 44

0.200.150.100.050.00

f43

Pasadena, CA(CalNex)

Riverside, CA (SOAR)

HOA-DHOA-NDSV-OOALV-OOA Avg. SOAR Avg. CalNex

f44 vs. f43 plot (with PMF Results)

60

50

40

30

20

10

0

Mas

s C

onc.

(µ

g/m

3)

5/21/2010 5/31/2010 6/10/2010

Date and Time (PDT)

SMPS UHSAS AMS + BC

AMS Comparison with SMPS, UHSAS (Part 1)


60

50

40

30

20

10

0

AM

S +

Aet

halo

met

er M

ass

Con

c. (

µg

m-3

)

6050403020100

SMPS Mass Concentration (µg m-3

)

1:1 Line Linear ODR Fit

Slope=1.02

r2=0.76

5/21/2010 5/31/2010 6/10/2010

Date and Time (PDT)

60

50

40

30

20

10

0

AM

S +

Aet

halo

met

er M

ass

Con

c. (

µg

m-3

)

6050403020100

UHSAS Mass Concentration (µg m-3

)

1:1 Line Linear ODR Fit

Slope=0.99

r2=0.73

5/21/2010 5/31/2010 6/10/2010

Date and Time (PDT)


Calculated Mie Scattering vs. CAPS (Part 1)

250

200

150

100

50

0

Ext

inct

ion

(Mm

-1)

5/21/2010 5/31/2010 6/10/2010Date and Time (PDT)

CAPS Extinction (630 nm)Calculated Scattering (SMPS)

250

200

150

100

50

0

Cal

c. M

ie S

catte

ring

[Mm

-1]

250200150100500

CAPS Extinction [Mm-1

]

Linear FitSlope=1.01

r2= 0.88

Calculated Mie Scattering vs. CAPS (Part 2)

30

25

20

15

10

5

0

AM

S O

rgan

ic M

ass

(g/

m3)

302520151050

OC (g/m3)

AMS vs. OC PM2.5

AMS vs. OC PM1

Linear ODR Fitslope=1.7

R2=0.78 (0.76 for PM2.5)

5/21/2010

5/31/2010

6/10/2010

TIm

e (PD

T)

AMS OM vs. Sunset Online OC

•Online Sunset OC data was corrected by multiplying the data by 2.57. This value was calculated from correlation plots of online and HiVol OC data. Without this correction the (AMS OM):(online OC) is unrealistically high.

30

25

20

15

10

5

0

AM

S O

rgan

ic M

ass

(µg

m-3

)

302520151050

FTIR Organic Mass (µg m-3

)

Linear ODR Fit

slope = 1.13, r2=0.44

1:1<14 h collection All periods

25

20

15

Tem

p

25

20

15

10

5

0

OM

Mas

s C

once

ntra

tion

(µg

m-3

)

5/16/2010 5/21/2010 5/26/2010 5/31/2010 6/5/2010 6/10/2010 6/15/2010

Date and Time (UTC)

FTIR Organic Matter Concentration AMS Organic Matter Concetration

Comparison of AMS OM vs FTIR OM (Russell Group UCSD)

30

25

20

15

10

5

0

Ma

ss C

onc

ent

ratio

n (

µg

m-3

)

5/16/2010 5/21/2010 5/26/2010 5/31/2010 6/5/2010 6/10/2010 6/15/2010Date and Time (UTC)

AMS (Univ. CO) TAG-AMS (Aerodyne)

30

25

20

15

10

5

0

TA

G-A

MS

Org

Mas

s C

onc.

(µ

g m

-3)

302520151050

CU AMS Org Mass Conc. (µg m-3

)

Org 1:1 Linear ODR Fit

slope = 1.19

r2 = 0.89

5/21/2010

5/26/2010

5/31/2010

6/5/2010

6/10/2010

6/15/2010

Da

te and T

ime (U

TC

)

Comparison Plots: TAG-AMS OM (Aerodyne) vs. AMS OM (Univ. CO.)

Comparison Weekday vs. Sunday – HOA Components & Tracers

References on Weekday/Weekend Effect in LA-area: Millstein et al. Atmos. Environ. 2008, 42, 632. Marr et al. Atmos. Environ. 2002, 36, 2327.

2.0 2.0

1.5 1.5

1.0 1.0

0.5 0.5

0.0 0.0HO

A-D

(µ

g m

-3)

00:00 12:00

Weekday (PDT)

00:00 12:00 00:00

Sunday (PDT)

360 360

320 320

280 280

240 240CO

(pp

bv)

1000 1000

800 800

600 600

400 400BC

(ng

m-3

)

3.0 3.0

2.0 2.0

1.0 1.0

0.0 0.0

HO

A-N

D (

µg

m-3

)

Solid – MeanDashed – Median

Aerosol Composition in Los Angeles During the 2010 CalNex Campaign Studied by High Resolution...

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