Four research flights were conducted

using NASAs DC-8 (airborne laboratory)

Whole air samples were collected in over 300

cans
Each can was analyzed for 75 Volatile
Organic Compounds (VOCs)

1.

2.

Research Goals
Can the data be simplified
mathematically to characterize sources
of VOCs?
What are the emission profiles for Los
Angeles and the Central Valley?

Sta$s$cs and linear algebra

Used to group related variables into weighted
components
Goal: turned 75 VOC measurements into 75 dierent
components/sources

Data preprocessed and

normalized in MATLAB
PCA performed using Mystat

Combina$ons of source proles add up to the background

Liquid Petroleum Gas and Exhaust Samples
LPG values normalized to ambient city propane values and
exhaust samples normalized to ethyne values

i-Pentane

n-Pentane

1-Butene

c-2-Butene

t-2-Butene

i-Butene

n-Butane

i-Butane

Propene

Propane

Ethyne

Ethene

Ethane

Relative Concentrations

LPG
Ambient
Exhaust

Blake and Rowland 1995, Science

Components have scores

Scores measure components descrip$on of the original data
"Variance" Explained by Rotated Components
1
2
3
4
11.077

2.106

1.864

1.783

2.378

1.349

Percent of Total Variance Explained

1
2
3

5.325

5.095

6.795

3.853

31.649

22.857

6.017

Signicant components are read into factors

Threshold variable |loadings| .5
Read the signicant variables in a column to determine a source
(H. Guo et al. 2004; Mintz and McWhinney 2008)

Example:
Variables
CH4 (ppmv)
CO2 (ppmv)
CO (ppbv)
OCS (MS)
HFC-152a (MS)

Factor 1
0.260
0.496
0.134
-0.127
0.079

Factor 2
0.743
0.022
0.832
0.037
0.616

Factor 3
0.360
-0.090
-0.146
-0.159
0.286

Factor 4
0.019
0.170
0.025
-0.909
0.020

Factor 5
0.190
-0.057
0.076
0.077
-0.145

Factor 6
-0.096
0.504
-0.157
-0.028
0.545

Factor 7
0.137
0.144
0.051
0.113
-0.151

Variables
CH4 (ppmv)
CO2 (ppmv)
CO (ppbv)
OCS (MS)
HFC-152a (MS)

Factor 1 Factor 2 Factor 3 Factor 4 Factor 5 Factor 6 Factor 7

0.743
0.504
0.832
-0.909
0.616
0.545

Variables
CH4 (ppmv)
CO2 (ppmv)
CO (ppbv)
HFC-134a (MS)
HCFC-22 (MS)
HCFC-142b (MS)
HCFC-141b (MS)
HFC-152a (MS)
CHCl3 (C/D)
CCl4 (C/MS)
CH2Cl2 (C/D)
C2Cl4 (C/MS)
C2HCl3 (D)
CH3Br (C/MS)
CH3I (C/D)
CH3CCl3 (C)
CH2Br2 (D)
CHBrCl2 (D)
CHBr2Cl (C/D)
EtONO2 (C/D)
i-PrONO2 (C/D)
n-PrONO2 (C)
2-BuONO2 (C)
3-PeONO2 (C/D)
2-PeONO2 (D)
3-Methyl-2-buONO2 (C)
Ethane (E)
Ethene (E)
Ethyne (E)
Propane (E/B)
Propene (E)
i-Butane (E/B)
n-Butane (E)
i-Pentane (E)
n-Pentane (E/B)
n-Hexane (E)
Isoprene (E/B)
n-Heptane (E/B)
n-Octane (B)
2,2-Dimethylbutane (B)
2,3-Dimethylbutane (B)
Cyclopentane (B)
Methylcyclopentane (B)
Cyclohexane (B)
Benzene (E/MS)
Toluene (B/MS)
Ethylbenzene (MS)
m/p-Xylene (MS)
o-Xylene (MS)
Acetaldehyde (MS)
Ethanol (MS)
Acetone (MS)

Factor 1

Factor 2

0.738
0.764
0.751
0.657

0.746
0.742
0.644
0.742
0.611
0.763
0.607
0.842
0.796
0.913
0.951
0.926
0.941
0.920
0.911
0.909
0.693

Factor 3

0.629

0.533
0.693
0.520

0.669

25.2% total variance

CO, Ethyne = Incomplete combusPon
Alkyl nitrates, Acetaldehyde = Photochemistry
CHBrCl2, CHBr2Cl = Water treatment
Methane, Ethane, Propane, i-Butane = Natural

0.861
0.754
0.665
0.664

0.690
0.900
0.708
0.792
0.773
0.827
0.854
0.876
0.905

0.726
0.781
0.844
0.874
0.797
0.754
0.779
0.802
0.852
0.840
0.693
0.762
0.822

Factor 1

gas

Factor 2
37.4% total variance
Alkanes, Cyclo-alkanes = Fossil Fuel

EvaporaPon
Ethene, Propene, Toluene, Xylenes = Industrial

Variables
CH4 (ppmv)
CO2 (ppmv)
CO (ppbv)
HFC-134a (MS)
HCFC-141b (MS)
HFC-152a (MS)
CHCl3 (C/D)
CCl4 (C/MS)
CH2Cl2 (C/D)
C2Cl4 (C/MS)
C2HCl3 (D)
CH3Br (C/MS)
CH3I (C/D)
CH3CCl3 (C)
CHBrCl2 (D)
CHBr2Cl (C/D)
CHBr3 (C/D)
EtONO2 (C/D)
i-PrONO2 (C/D)
n-PrONO2 (C)
2-BuONO2 (C)
3-PeONO2 (C/D)
2-PeONO2 (D)
3-Methyl-2-buONO2 (C)
Ethane (E)
Ethene (E)
Ethyne (E)
Propane (E/B)
Propene (E)
i-Butane (E/B)
n-Butane (E)
i-Pentane (E)
n-Pentane (E/B)
n-Hexane (E)
n-Heptane (E/B)
n-Octane (B)
2,2-Dimethylbutane (B)
2,3-Dimethylbutane (B)
Cyclopentane (B)
Methylcyclopentane (B)
Cyclohexane (B)
Benzene (E/MS)
Toluene (B/MS)
Ethylbenzene (MS)
m/p-Xylene (MS)
Acetaldehyde (MS)
Ethanol (MS)
Acetone (MS)

Factor 1

Factor 2

Factor 3

0.783
0.608
0.833
0.782
0.759
0.881
0.849

0.774
0.734

0.796
0.886

0.615

Factor 4

-0.507

0.428
0.718

83.1% total variance

0.864
0.517
0.871

0.964
0.966
0.936
0.925
0.918
0.946
0.803
0.876
0.701
0.644

0.710
0.893

0.608

0.746
0.829
0.827
0.869
0.873
0.929
0.881

0.641
0.877
0.898
0.823
0.735
0.887
0.929
0.710
0.828
0.898

Combus$on
Photochemical produc$on
Fossil fuel evapora$on
Water treatment
Natural gas
Industrial

Factor 3
4.5% total variance

0.821

0.835

Factors 1 and 2 (same as LA and

Inland Empire combined)

CH3I, CHBr3 = Oceanic

Oceanic source observed in only west samples

Variables
CH4 (ppmv)
CO2 (ppmv)
CO (ppbv)
OCS (MS)
HFC-152a (MS)
CCl4 (C/MS)
C2Cl4 (C/MS)
C2HCl3 (D)
CH3Br (C/MS)
CHBrCl2 (D)
CHBr2Cl (C/D)
i-PrONO2 (C/D)
n-PrONO2 (C)
2-BuONO2 (C)
3-PeONO2 (C/D)
2-PeONO2 (D)
3-Methyl-2-buONO2 (C)
Ethane (E)
Ethene (E)
Ethyne (E)
Propane (E/B)
Propene (E)
i-Butane (E/B)
n-Butane (E)
i-Pentane (E)
n-Pentane (E/B)
n-Hexane (E)
n-Heptane (E/B)
n-Octane (B)
2,2-Dimethylbutane (B)
Methylcyclopentane (B)
Benzene (E/MS)
Toluene (B/MS)
Acetaldehyde (MS)
Ethanol (MS)

Factor 1

Factor 2

0.599
0.817
0.866

0.743

Factor 3

Factor 4

Factor 5

Factor 6

Factor 7

0.504

-0.909
0.616

0.545
0.778

0.845
0.629

Octane),
Methylcyclopentane = Oil
drilling evaporaPon
Alkyl nitrates,
Acetaldehyde =
Photochemistry

0.890
0.902
0.631

0.643

0.720
0.734

0.710

0.574

0.677

0.630

0.901
0.573

0.657

0.848
0.880
0.886
0.932
0.959

0.820
0.916

Factor 2

22.9% total variance

0.731
0.646
0.545
0.910
0.655
0.631
0.520

Factor 1
31.6% total variance
Alkanes (not including n-

0.832

0.699
0.888

CO, Ethyne = CombusPon

CH4, Alkyl nitrates,

Toluene = Dairies,
Agriculture

Variables
CH4 (ppmv)
CO2 (ppmv)
CO (ppbv)
OCS (MS)
HFC-152a (MS)
CCl4 (C/MS)
C2Cl4 (C/MS)
C2HCl3 (D)
CH3Br (C/MS)
CHBrCl2 (D)
CHBr2Cl (C/D)
i-PrONO2 (C/D)
n-PrONO2 (C)
2-BuONO2 (C)
3-PeONO2 (C/D)
2-PeONO2 (D)
3-Methyl-2-buONO2 (C)
Ethane (E)
Ethene (E)
Ethyne (E)
Propane (E/B)
Propene (E)
i-Butane (E/B)
n-Butane (E)
i-Pentane (E)
n-Pentane (E/B)
n-Hexane (E)
n-Heptane (E/B)
n-Octane (B)
2,2-Dimethylbutane (B)
Methylcyclopentane (B)
Benzene (E/MS)
Toluene (B/MS)
Acetaldehyde (MS)
Ethanol (MS)

Factor 1

Factor 2
0.743

Factor 3

0.832
0.616
0.845
0.629

0.631
0.599

0.720
0.734

0.817
0.866
0.710

0.574

0.677

0.630

Factor 4

Factor 5

-0.909

0.890

Factor 6
0.504

0.545
0.778

0.902
0.643

Factor 7

5.3% total variance

OCS, CH3Br = Fumiga$on
(Weller and Morton 2001)

CHBrCl2, CHBr2Cl = Water

0.657

0.848
0.880

treatment

0.886
0.932
0.959

0.820
0.916
0.731

Factor 7

7.7% total variance

0.646
0.545
0.910
0.655
0.631
0.520

Factor 5
5.1% total variance

0.901
0.573

Factor 4

0.699
0.888

Ethene, Propene,

Benzene = Industrial

Los Angeles

Central Valley

Total variance

Total variance

3 separable factors

5 separable factors

Ground samples of background and near sources

would improve PCA factors
Use photochemical box models with PCA results on
source characteriza$ons
How much ozone produc$on is associated with each VOC

emission source?

Posi$ve Matrix Factoriza$on (PMF) compared to

PCA
Leuchner and Rappenglck 2009, Atmospheric
Environment

Dr. Donald Blake

Josele Marrero
Jennifer Broughton
Dr. Emily Schaller
Rick Sheler
NASA
NSERC
UND