ALmospherlc sclences Whole Alr

8afe uay's 6
Lh
SA8Þ paruclpauon

A|r qua||ty mon|tor|ng and
VCC measurements |n
g|oba| ecosystems:
- kemote background |ocanons
- Þaclñc 8asln
- Areas w|th spec|a| cond|nons
- Marlne envlronmenLs
- AgrlculLural wasLe
- Cll sands
- 8lomass burnlng, eLc.
- Wor|d's megac|nes
- Mexlco ClLy
- Pong kong
- karachl
- Mecca, eLc.
Pristine
Polluted
UC Irv|ne kow|and-8|ake WAS group
Vo|an|e organ|c compound (VCC) sources
8|ogen|c:
- lsoprene
- !-Þlnene
- "-Þlnene
8|omass burn|ng:
- LLhyne
- 8enzene
- #-8uLane
Industr|a|:
- C
2
Cl
4
- PClC-22
- PlC-134a
Ioss|| fue| combusnon:
- LLhyne
- 8enzene
- LLhene
Ioss|| fue| evaporanon:
- MeLhane
- $-ÞenLane
nydrocarbon ox|danon:
- 2-8uLyl nlLraLe
- AceLaldehyde
Cceans:
- MeLhyl nlLraLe
- MeLhyl lodlde
Rowland-Blake Lab Analytical Capabilities

UC-Irvine laboratory
Trace gas analysis (canisters)

• Gas Chromatography (GC)
• Flame Ionization Detection (FID)
• Electron Capture Detection (ECD)
• Mass Spectrometric Detection (MSD)
Sensitive, speciated
VOC detection
• Identification and quantification
of >100 VOCs (and thousands of cans)
LOD Accuracy Precision
NMHCs 3 ppt 5% 2%
Halos 10 ppq 5% 1%
Alkyl-NO3 10 ppq 10% 1%
DMS 1 ppt 5% 1%
OCS 10 ppt

5% 2%
Sample LCu ChromaLogram
Time (min)
R
e
s
p
o
n
s
e

(
m
V
)

0 1.0 2.0 3.0 4.0 3.0 6.0 7.0 8.0 9.0 10.0 11.0 12.3
0
10.0
20.0
30.0
40.0
30.0
mv
mln
P
-
1
2
1
1

C
l
C
-
1
1

C
l
C
-
1
1
3

C
P
3
l

C
P
2
C
l
2

M
e
L
h
y
l

n
l
L
r
a
L
e

C
P
C
l
3

L
L
h
y
l

n
l
L
r
a
L
e

C
2
C
P
C
l
3

$
-
Þ
r
o
p
y
l

n
l
L
r
a
L
e

C
P
8
r
C
l
2
#
-
Þ
r
o
p
y
l

n
l
L
r
a
L
e

C
2
C
l
4

2
-
8
u
L
y
l

n
l
L
r
a
L
e

3
-
Þ
e
n
L
y
l

n
l
L
r
a
L
e

/

2
-
Þ
e
n
L
y
l

n
l
L
r
a
L
e

C
P
8
r
3

nydrocarbons
! Cn
4
: greenhouse gas
! 1ropospher|c
C
3
precursors

- meLhane
- eLhane
- eLhene
- eLhyne
- propane
- propene
- propyne
- $-buLane
- #-buLane
- %-2-buLene
- &-2-buLene
- 1-buLene
- $-penLane
- #-penLane
- #-hexane

na|ocarbons
! CICs: strong
greenhouse gases
! Many: stratospher|c
C
3
dep|etors
- ClC-11
- ClC-12
- ClC-113
- ClC-114
- CCl
4


- CP
3
CCl
3


- P-1211
- P-2402
- PClC-141b
- PClC-142b
- PClC-22
- PlC-134a
- 1,2-uCL

Carbon monox|de
! Urban a|r po||utant
! Decreases g|oba| Cn

Su|fur compounds
! C|oud condensanon nuc|e|
! Añect g|oba| a|bedo

- uMS
- uMuS
Crgan|c n|trates
! 1ransport NC
x
(= NC + NC
2
)
! NC
x
= trop. C
3
precursor

- MeCnC
2

- LLCnC
2

- 1-ÞrCnC
2
- 2-ÞrCnC
2

Some compounds and
their atmospheric effects
- C
2
Cl
4

- C
2
PCl
3

- CPCl
3

- CP8r
3

- CP
2
Cl
2

- CP
2
8r
2

- CP8rCl
2

- CP8r
2
Cl
- CP
3
Cl
- CP
3
8r
- CP
3
l
- C
2
P
3
l
- eLc.
- 2-8uCnC
2

- 2-ÞeCnC
2

- 3-ÞeCnC
2

- CCS
- CS
2

- benzene
- Loluene
- lsoprene
- sLyrene
- (-xylene
- )-xylene
- *-xylene
- 1,3,3-1M8
- 1,2,4-1M8
- 1,3-buLadlene
- %-2-penLene
- &-2-penLene
- #-ocLane
- #-nonane
- eLc.
WAS group quesuons/pro[ecLs
• 1. uoes fracklng have a speclñc vCC proñle
• 2. lf fracklng has a speclñc vCC proñle ls lL
evldenL ln Lhe LA 8asln
• 3. Are Lhere locauons ln Lhe LA 8asln LhaL
exhlblL l-penLane/n-penLane rauos LhaL dlñer
from gasollne evaporauon
• 4. Can we see phoLochemlcal evoluuon of
coasLal alr ln Lhe lnland Lmplre alr
• 3. Pow lmporLanL are marlne vCC emlsslons
on Lhe Los Angeles basln alr quallLy
• 6. Are Lhere cerLaln areas of Lhe LA 8asln LhaL
emlL proporuonally more greenhouse gases
• 7. Pow do 2014 greenhouse gas levels ln Lhe LA
8asln compare wlLh Lhose observed durlng
nASA's A8C1AS pro[ecL ßown ln 2008 and
prevlous SA8Þ mlsslons
• 8. uslng alrcraû daLa can we deLermlne lf
meLhyl bromlde ls sull belng used for sLrucLural
fumlgauon for LermlLes ln Lhe LA 8asln

• 9. Pave CvCC emlsslons from dalrles changed durlng
Lhe pasL ñve years
• 10. Can we esumaLe meLhane emlsslons from dalrles
ln Lhe cenLral valley. C&nC?
• 11. Can we use alrborne daLa Lo valldaLe ML. Wllson
hourly daLa
• 12. use ML. Wllson daLa Lo esumaLe greenhouse gas
emlsslons from Lhe LA 8asln
Whole Alr Sampllng group members wlll learn Lhe
lmporLance of and paruclpaLe ln:
Þreparauon of canlsLers for whole alr sampllng
ulscusslons of prevlous alrborne and ground based sLudles
lllghL plannlng-where Lo ñll canlsLers
Chemlcal analysls of samples
ChromaLogram modlñcauon
uaLa preparauon
MeLhods of daLa lnLerpreLauon

SA8Þ MenLor !oseue Marrero
ALmospherlc chemlsL by day
Super-Lady-World-Saver by nlghL
Croup meeung
1ube bendlng = humlllauon
1ube bendlng = humlllauon
Movlng snakes on and oñ Lhe uC-8
WAS sampllng
MeLhane analysls aL uCl
CC & CC
2
analysls aL uCl
lleld Lrlp WAS sampllng-ML Wllson from Þasadena
MWC
MWC Crounds
CA88/!ÞL SlLe
Mount W||son
0
5
10
15
20
25
30
35
40
45
50
39198 39200 39202 39204 39206 39208 39210
Jiulian Time
C
2
H
C
l
3
,

p
p
t
v
Mount W||son
0
20
40
60
80
100
120
39198 39200 39202 39204 39206 39208 39210
Jiulian Time
C
2
C
l
4
,

p
p
t
v
LLhane (ppL) vs meLhane (ppm) for
four one week perlods aL ML. Wllson
0
2000
4000
6000
8000
10000
12000
1.7 1.75 1.8 1.85 1.9 1.95 2 2.05 2.1 2.15 2.2
LLhane (ppL) vs meLhane (ppm) for
four SA8Þ 2013 ßlghLs
0
1000
2000
3000
4000
3000
6000
1.7 1.73 1.8 1.83 1.9 1.93 2 2.03 2.1 2.13 2.2
Vo|an|e Crgan|c Compounds |n the atmosphere
VCCs
Cn
nC
2
NC

NC
2
C + C
2
C
3
Cxygenated VCCs Secondary organ|c aeroso| (SCA)
VCCs
+,-./ 0001%2-(10$3%1-45653-.367-5&%26 8#4
00019).718%1576$#3&63%$6+:;6<8%7=.4>?@-36?=5.-A1=$B
kC
2
kC
VCC reacnons |ead to:
- 1ropospherlc ozone (C
3
)
- Secondary organlc aerosol (SCA)
1hese products |mpact:
- Alr quallLy, global cllmaLe, healLh
Some VCCs are tox|c:
- e.g. 8enzene ls carclnogenlc
C
2


C
2


VCCs
NC
x

SC
2

VCCs
NC
x

VCCs
NC
x

numan hea|th eñects of exposure to ozone (C
3
)
2C*/660001-*81=)D68*E6)F)#-2-8@&26*)*5@8E)#12&(@
2C*/660001-*81=)D6=@)62-8@&212&(@
Number of peop|e añected
S
e
r
|
o
u
s
n
e
s
s

o
f

e
ñ
e
c
t

1yp|ca| ozone |eve|s:
- Þre-lndusLrlal: 10-13 ppbv
- Clean alr: 30-40 ppbv
- ÞolluLed alr: 80-130 ppbv
Czone añecL on people and anlmals
Czone lmpacL on planL yleld
Ma[or LqulpmenL
• Chassls uynamomeLer
- consLanL dlluuon sampllng
• vMAS
- raw sample
• CanlsLer
- raw sample
• ÞroLon 1ransfer 8eacuon - Mass SpecLromeLer
(Þ18-MS)
- dlluLed sample
LÞC vehlcles 1esung Sequence
1
sL
1esL: 8asellne

2
nd
1esL: new caLalyuc converLer, C
2
sensor,
LC8 valve w/o Alr/luel rauo Lunlng

3
rd
1esL: new caLalyuc converLer, C
2
sensor, LC8
valve aûer Alr/luel rauo Lunlng
Taxi (FF1883) Emissions
Before and After Repair
0
1
2
3
4
5
6
NOx + HC CO
E
m
i
s
s
i
o
n

(
g
/
k
m
)
Baseline
New Converter, O2 sensor, EGR #1
New Converter, O2 sensor, EGR #2
New Converter, O2 sensor, EGR + Tuning
Emission Limit
Emission Limit
!
"!
#!
$!
%!
&!!
&"!
&#!
&$!
&%!
'()*+,-+* )./0*+* 1,2*+* )./0-+* +(34,-+*
5
6
*
.
-
7
*

9
'
:
'
+
7

.
-
,
'
/
;

0
0
9
6
).*</+6*.,*. )/=,</+6*.,*.
LxpecL very llule change ln l-penLane
because noL much from Laxls
LxpecL very llule change ln l-penLane because
noL much from Laxls
!
"!!
#!!
$!!
%!!
&!!
'!!
(!!
)!!
*!!
+,-./01/. -234./. 506./. -2341/. /,7801/. 9:;
<
=
.
2
1
>
.

@
+
A
+
/
>

2
1
0
+
3
B

4
4
@
=
-2.C3/=.20.2 -3D0C3/=.20.2
Þropane + buLanes/penLanes for SepLember 2013-
March 2014
uaLa from LÞu roadslde program
y = -0.032x + 1248

0
3
10
13
20
23
30
33
40
43
41320 41340 41360 41380 41600 41620 41640 41660 41680 41700 41720 41740
Þropane & buLanes/penLanes for May 2013-lebruary
2014
8ealume uaLa from Mongkok
y = -0.03Sx + 1480

0
20
40
60
80
100
120
140
160
180
200
41380 41430 41480 41330 41380 41630 41680
Mk
nCx for May 2013-lebruary 2014 8ealume uaLa
from Mongkok
y = -0.16x + 7003

0
100
200
300
400
300
600
41380 41430 41480 41330 41380 41630 41680
Mk
ÞoLenual ozone formauon ln Pong kong based on 60 grld
samples from SepLember 2013 and 60 ln lebruary, 2014
0
100
200
300
400
300
600
700
800
900
1000
1oLal Ml8
M
l
8
2013 2014
- 9.4°
Mk SLauon
-3.00
0.00
3.00
10.00
13.00
20.00
23.00
!an leb Mar Apr
C
o
n
c
e
n
L
r
a
u
o
n

(
p
p
b
)

C3 (ppb)
2012
2013
2014
vCC/nCx for May 2013-lebruary 2014 8ealume
uaLa from Mongkok
y = -0.004x + 1SS

0
3
10
13
20
23
30
41330 41400 41430 41300 41330 41600 41630 41700 41730
Mk
Czone formauon dependence on nCx and
vCC concenLrauons
nASA A8C1AS
!une-!uly, 2008
• 12 ßlghLs on Lhe nASA uC-8
• 1631 whole alr samples collecLed
• lllghLs ln and around Los Angeles
phoLochemlsLry and CPC emlsslons (ßlghL 13)
• lllghLs ln Canada for blomass burnlng
8enzene (ppLv) vs CC (ppbv)
Þropane vs CC (LÞC)
PClC-134a vs ume (urban)
C2Cl4 vs ume (solvenLs)
1,3-buLadlene vs ume (blomass
burnlng)
Þropyne vs ume (blomass 8)
luran vs ume (blomass 8)
Biomass burning plume sampled near Tahiti
September 5, 1996 
Modified from Browell et al., 1999 and Blake et al., 1999
10-Day Backwards Trajectories arriving near Tahiti
September 5, 1996
- Pollution plume came all the way from biomass burning in Africa
Modified from Blake et al., 1999
1oluene vs CC (solvenLs)

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