Goldstein ARB Chair's seminar July 1, 2008
Transcript of Goldstein ARB Chair's seminar July 1, 2008
Hourly In-Situ Quantification of
Organic Aerosol Marker Compounds
Allen Goldstein
University of California at Berkeley
ARB Chair’s Seminar Series July 1, 2008
Brent Williams, Angie Miller, UC Berkeley
Nathan Kreisberg, Susanne Hering, Aerosol Dynamics Inc.
Photo by Mike Cubison (U.Colorado-Boulder)
ACKNOWLEDGEMENTS
Funding California Air Resources Board (ARB award 03-324)
ARB Staff Support Nehzat Motallebi, William Vance, Eileen McCauley, Chris Jakober
SOAR Host Paul Ziemann (UC Riverside)
SOAR Coordinator Ken Docherty (University of Colorado Boulder)
Operation of Goldstein mobile lab Angela Miller, Megan McKay (UC Berkeley)
SOAR Participants Ziemann et al., Prather et al., Jimenez et al., Worsnop et al., Schauer et al.,
Hannigan et al., Eatough et al., Weber et al., Arey et al., Fitz et al., Paulson et al., etc.
Overview Quantification of organic marker compounds • Motivation- importance of organic aerosols • Organic aerosol measurement approaches • New in situ instrument
– Thermal desorption Aerosol GC/MS – TAG
• Study of Organic Aerosol in Riverside (SOAR) • TAG in action: hourly measurements of marker
compounds and resolution of source contributions
Further TAG developments (if time allows) • Semi-volatile phase partitioning (SV-TAG) • Introduction of multidimensional GC (2D-TAG)
ObjectiveHourly measurements of organic marker compounds in
ambient aerosols.
Science QuestionsWhat are the major sources for organic aerosols?
How important is secondary organic aerosol (SOA), andwhat are its composition and transformation pathways?
Motivation Regulatory efforts to attain fine particulate matter (PM2.5)
standards require improvements in our knowledge of the factors controlling PM concentration, size, and chemical composition. Organics are typically the largest and least understood fraction of PM.
Objective Hourly measurements of organic marker compounds in
ambient aerosols.
Science Questions What are the major sources for organic aerosols?
How important is secondary organic aerosol (SOA), and what are its composition and transformation pathways?
Aerosols impact climate and health
Ganges River, IndiaGanges River, India
““Asian Forecast: Hazy, WarmerAsian Forecast: Hazy, Warmer—— Clouds of pollution heat lowerClouds of pollution heat lower atmosphereatmosphere””
L.T. M
olina, MIT
N. Marley, Univ. of Arkansas
J. A
llen/
NA
SA
Mexico CityMexico CityLos Angeles, CALos Angeles, CA
Long~lived greenhouse gases
I Halo carbons
Climate efficacy
1'.0
1.0 - 1.2
(see caption)
- 10 -100 yrs
Ozone Stra ospheric Tropospheric 0.5 - 2 .0 Weeks ·to
"1 00 yrs
Stratospheric water vapour from CH4
Surface albedo
{
Direct effect
Total Aerosol Cloud a.lbedo
ef1ect
Linear contrai!s
Solar irradiance
J (-0.05) I I
Land use I
Black carbon on snow
(0.01 }
-2 -1 0 Radiative Forcing
~1.0 10 years
10 -100 yrs
0.7 - 1.1 Days
1.0 - 2 .0 Hours -Days
~ 0.6 Hours
0.7 - 1.0 10 -100 yrs
2 Timescale
Global High
Global High
Continental Med
to global
Global Low
Local to Med continental - Low
Continental Med togloba.l - Low
ConUnen al Low to global
Continental Low
Global Low
Scientific understanding
Radiative forcing of climate between 1750 and 2005
Intergovernmental Panel on Climate Change (2007) Working Group I: The Physical Science Basis of Climate Change
Long~lived greenhouse gases
Ozone
Stratospheric water vapour from CH4
Surface albedo
{
Direct effect
Total Aerosol Cloud a.lbedo
ef1ect
Linear contrai!s
Solar irradiance
-2
Stra ospheric J (-0.05) I I
Land use
(0.01 }
-1 0 Radiative Forcing
Climate efficacy
1'.0
1.0 - 1.2 I
Halo carbons
Tropospheric 0.5
0.
1.0 - .
o.·
(see caption)
- 10 -100 yrs
Days
Global High
Global High
to global
Hours Continental Low
Radiative forcing of climate between 1750 and 2005
Ch. 2 summary: “The total direct aerosol [radiative forcing] as derived from models and observations is estimated to be –0.5 [±0.4] W/m2, with a medium-low level of scientific understanding”
AEROSOLS
MATTER!
Intergovernmental Panel on Climate Change (2007) Working Group I: The Physical Science Basis of Climate Change
Organic aerosol is typically largest fraction (Tropospheric non-refractory PM1 via Aerosol Mass Spectrometer)
“Ubiquity and Dominance of Oxygenated Species in Organic Aerosols in Anthropogenically-Influenced Northern Hemisphere Midlatitudes”, Zhang et al. Geophysical Research Letter, 34 (2007)
Org 2-SO4 -NO3
+NH4
Organic aerosol Characterization methods
Sampling method continuum
bulk ���� size classified ���� single particle
Organic aerosol Characterization methods
Sampling method continuum
bulk ���� size classified ���� single particle
filter impactor In-situ mass spectrometry
��� ���
Organic aerosol Characterization methods
Sampling method continuum
bulk � size classified � single particle
filter In-situ mass spectrometryimpactor
Characterization methods
• group properties – OC/EC, FTIR (bonds), water soluble OC
• molecular level – GC/MS, LC/MS, some single particle MS
Organic aerosol Characterization methods
Sampling method continuum
Characterization methods
• group properties – OC/EC, FTIR (bonds), water soluble fraction
• molecular level – GC/MS, LC/MS, some single particle MS (e.g. UVI)
In-situ mass spectrometry
Solvent extraction/ thermal desorption
bulk ���� size classified ���� single particle
filter impactor In-situ mass spectrometry
��� ���
Organic aerosol Characterization methods
Sampling method continuum
bulk � size classified � single particle
filter In-situ mass spectrometryimpactor
Manual collection Automated time – integrated sampling Time-resolved, continuous often on selected days only
No molecular level Detailed speciation possible characterization
Genesis of TAG: in-situ field instrument
Past PM2.5 organic measurements: In-Situ particle (no individual compound separation) Filter collection (12 to 24-hour time resolution)
Need an instrument capable of: Separating / Identifying / Quantifying individual organic marker compounds from ambient PM2.5 with hourly time resolution (to track diurnal changes)
Genesis of TAG: in-situ field instrument
Goldstein et al. methods for VOCs:
“In situ measurements of C2-C10 volatile organic compounds
above a Sierra Nevada ponderosa pine plantation”
M.S. Lamanna and A.H. Goldstein, J.Geophys. Res. 104 (1999)
“VOC measurements at Trinidad Head, CA …Analysis of sources,
atmospheric composition and aerosol residence times” D.B. Millet, A.H. Goldstein et al., J.Geophys. Res. 109 (2004)
Hering et al. methods for inorganic aerosols:
“A new method for the automated measurement of atmospheric fine particle nitrate”
M.R. Stolzenburg and S.V. Hering, Environ. Sci. and Technol. 34 (2000)
“Hourly concentrations and light scattering cross sections for fine particle sulfate at Big Bend National Park”
S.V. Hering et al. Atmospheric Environment 37 (2003)
TAG= Thermal desorption Aerosol Gas chromatograph (MS/FID)
Gas Chromatograph
Mass Spectrometer
6-port valve
Aerosol Collector &
Thermal Desorption Cell
Cyclone Precut (PM2.5)
Humidifier (adhesion)
Filter (field blank)
x
1
2 3 4
1. Collection technique:
– Inertial Impaction (30°C) 2. Sample transfer:
– Thermal Desorption (50-300°C ) 3. Chemical separation:
– Gas Chromatography 4. Compound quantification:
– Mass Spectrometry (and/or FID) 5. Compound identification:
– Spectrum + Retention Time Matching
TIC: RVR 392.DTIC: RVR 385.DTIC: RVR 394.D
TAG urban ambient data
500000
450000
400000
350000
300000
250000
200000
150000
100000
50000
0
>
_ _ _
Ambient Air
Pure Air
Filtered Air
Particle = Ambient – Filtered
20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Time Resolution: 1 hour Collection: 0.5 hour Sample Volume: 0.25 m 3
Thermal Desorption: 50-300 0C GC oven temp. range shown here: ~ 45 0C to 3000C
Resolved compounds will determine the aerosol source (i.e. markers)
Total Ion Abundance
0 i i I I ~ i i I I I ~ -!!:a= 2-F Ura nm eiha rlol ' · ' · · ' ' '
~-t?hthalic acidNicotine g r-
s g
Nicotyrine Levogl ucosane
1 ,2 diphenylcyclopropane
;o ~ ~ g
Myri sti c acid 1 ,4-0iphenyl-1 , 3-butadi ene
Hmdecaooic acid, methyl estec . . / I 11 I i i I i i 11 ~======::....::__:_:.::._£Palm1t1c acid / 8 .....
m ::, ..... 0 "-I ::, 0
::1 g 3 m --~- ~ ::, I
- g
~ g
~
g g
I
,' ~ ]":;:-:::=~ Cocaine
Oleic acid / i ~i:;;~~====~======~site;;aric acid / ~
~~~------ Docosane a1r=-Tricosane -------------------------------Tricosane
Tetracosane
Pentacosane Hexacosane ------------------------- 7
5 Heptacosane \ \
i
~ 8 ~ 8
Cyclic alkane? Octacosane ~ . = Non acosane
I
~ 8
""' Stigmasta~~j~~~d11Ane
~
t aryl l_a\.lr~ineitriacontane D01tnacontane
ritriaconta ne Tet ratriaco ntane
Hexatriaco ntane
Heptatri acontan e
I I I ~
8 I I I,
~ ~ I 8 ! \ "4 I !' ~ 8 I , I I ,
~8 I
' \
phen anthreneca rb oxylic acid ester
Benzly butyl phthalate
Eicosene T etracosa ne
=====-?
Z-12-Pentacose ne - Pentacosane
Dronabinol
~ ()
~ c
Bis(2-ehtylhexyl) p hthalate
::-=::::--- C~n nabi nol Hexacosane
TA
G
Ex
amp
le Ch
rom
ato
gram
B
erkeley
Am
bien
t Air
Feb
ruary
7, 2006 22:30-24:00
100’s of id
entifiab
le co
mp
ou
nd
s
TAG Applications To Date
• Field Sampling
– ICARTT 2004, Chebogue Point, Nova Scotia
• Ambient sampling downwind of United States and Canada
– SOAR 2005, Riverside, California
• Ambient sampling downwind of Los Angeles
– BEARPEX 2007, Blodgett Forest, California
• Ambient sampling within a forest canopy
– Pittsburgh Toxics Study 2008, Pittsburgh, Pennsylvania
• Ambient sampling within urban center
– Carnegie Mellon University
• Reaction chamber studies
020
060
010
000
24
68
100
510
15
020
0060
000
24
68
100
510
15221188 222200 222222 222244 222266 222288 221188 222200 222222 222244 222266 222288
Individual TAG Compounds vs. Aerosol Mass Spectrometer (AMS) Total Organics and Total SO4
2-
Chebogue Point Nova Scotia 2004 Compound: A Compound: B
4-Pentenoic acid, 2-acetyl-2,3-dimethyl-,ethyl ester
)(C11H18O3
TAG Compound A
218 220 222 224 226 228 Day of Year 2004
Event Type 2
Event Type 1 No SO4
Rel
ati
ve
Ab
un
da
nce
(dif
fere
nt
sca
les)
Rel
ati
ve
Ab
un
da
nce
(dif
fere
nt
sca
les)AMS SO4
1,6-Dioxaspiro[4,4]nonane-2,7-dione
(C7H8O4)
218 220 222 224 226 228 Day of Year 2004
Event Type 2
TAG Compound B
Event Type 1 No SO4
AMS Total Organics
SO4 SO4
AMS data (Aerodyne Research, Inc.: Worsnop et al.)
□ 0 .0000 - 0.0012
0 0 .0012 - 0.0018
0 0 .0018 - 0.0027
0 0 ,0027 - 0,0040
□ 0 .0040 - 0.0060
□ 0 .0060 - 0.0090
■ 0 .0090 - 0.0136
■ 0 .0136 - 0.0203
□ 0 .0203 - 0.0305
■ 0 .0105 - 0.0458
■ 0 .0458 - 0.0686
■ 0 ,0686 - 0,1030
■ > 0 .1030
Study of Organic Aerosols at Riverside (SOAR)
Location: University of California, Riverside
50 Miles : 80 Kilometers
Los Angeles Riverside
N
PM2.5 Gridded Emissions (short tons/ozone season day/grid cell)
NOAA http://map.ngdc.noaa.gov/website/al/emissions/Run.htm
SOAR 2005
2 Measurement Periods
• Summer (July 18 – August 15, 2005)
• Fall (October 28 – November 30, 2005)
Instrumentation
• Meteorological, radiation, trace gas, and aerosol measurements
• TAG, VOC-GC/MS, O3 (x2), CO (x2), NOx (x2), Aerodyne AMS (x5), Thermal desorption particle beam MS, ATOFMS (x3), CPC (x8), EC/OC (x2), PILS-WSOC, High Volume filter samplers (multiple), aethelometer (multiple), nephelometer (multiple), OPC, DMA, MAAP, SMPS (multiple), APS, TEOM (multiple),Hg speciation, DMT CCN, meteorological and radiation equipment
• See study website for more details: (http://cires.colorado.edu/jimenez-group/Field/Riverside05/)
a)
22000000 115500FFooccuuss PPeerriioodd4400
AAMM
SSOO
rrggaann
iiccss
((uugg
mm--33
))
115500003300
110000002200
5500001100
CCOO
((ppppbb
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ppbb))
110000
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b)
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AAMM
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330055
331100
331155
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DDaayy ooff YYeeaarr 22000055
SOAR Measurement Periods
a) Summer (July 17-August 15)
2000 150Focus Period40
AM
SO
rgan
ics
(ug
m-3
)
150030
100020
50010
CO
(ppb
)
CO
(ppb
)
100
50
0 0 0
195
200
205
210
215
Day of Year 2005 Fall (October 25-November 30)b)
325
220
330
225
335
AM
SO
rgan
ics
(ug
m-3
)
2000 150Focus Period40
150030 100
50 100020
50010
0 0 0
300
305
310
315
320
O3
(ppb
)
O3
(ppb
)
Day of Year 2005
Very different Photochemistry (and Meteorology)
\/ I✓ ._-... -1- _,. ,,,- \
/ I \_,, '-.z_ -----\
I '-... __ I __ _..
Summer Winds Fall Winds (11 days) (11 days)
N N
10 20
30 40
E W
S
S
5 10 15 20 25
EDay W
S
S
N N
Night W 5 10
15
E W 5 10 15 20 25
E
0.4 - 0.8 m/s 0.0 - 0.4 m/s 0.8 - 1.2 m/s >1.2 m/s Wind Speed = Frequency = Length of Wedge
SOAR TAG Measurements and Source Apportionment
• Resolved >300 organic marker compounds hourly
• Positive Matrix Factorization (PMF) – 128 of 300 resolved TAG organic compounds in Summer – 144 of 300 resolved TAG organic compounds in Fall
• Identified organic aerosol sources based on PMF groupings – 8 in Summer – 7 in Fall
San Francisco Bay
Northern CaliforniaNorthern California Sept. 6, 2007Sept. 6, 2007
‘Lick’ fire
‘Moonlight’ fire
Marker compounds for source identification
Wood combustion ~ retene
800
750
700
650
600
550
500
450
400
350
300
250
200
150
100
219 m/z
234 m/z
33.80 33.85 33.90 33.95 34.00 34.05 34.10 34.15 34.20 34.25 34.30 34.35
Bangkok
222111000 222111222 222111444 222111666 222111888 222222000
Examples of marker compounds for source
Motor vehicles ~ hopanes, steranes identification
Bangkok
Riverside
C30H52 MW 413
17α(H),21β(H)-30-Norhopane
210 212 214 216 218 220 Day of Year 2005
Day of Year 2005
28no
r17b
etah
.hop
ane
210 212 214 216 218 220210 212 214 216 218 220210 212 214 216 218 220
000111000
000000000000
222000000000
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elat
ive
Abu
ndan
ce
8/10
12-Hour Filter Collection Simulation
Riverside, 2005
0 10
0000
20
0000
30
0000
40
0000
210 212 214 216 218 220
7/29
7/30
7/31
8/01
8/02
8/03
8/04
8/05
8/06
8/07
8/09
Hourly (TAG) data captures dynamics missed by 12 hour filter collections
17α(H),21β(H)-30-Norhopane (Vehicle Emission Marker)
Day of Year 2005
28no
r17b
etah
.hop
ane
210 212 214 216 218 220210 212 214 216 218 220210 212 214 216 218 220
000111000
000000000000
222000000000
000000333000
000000000000
444000000000
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Abu
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0 10
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20
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210 212 214 216 218 220
7/29
7/30
7/31
8/01
8/02
8/03
8/04
8/05
8/06
8/07
8/09
Riverside, 2005
Time resolved data captures dynamics
Large morning maxima Multiple maxima
within 12-hours
17α(H),21β(H)-30-Norhopane (Vehicle Emission Marker)
Riverside, CARiverside, CA
Biogenic vs.
Anthropogenic Alkanes
]2
)([
31
25
11
∑ =
+− +−= n
nn nwax
CCCC
Adapted from Simoneit 1989 J.Atmos.Chem.
SUMMER
0% 20% 40% 60% 80%
100%
210
211
212
213
214
215
216
217
218
219
220
Day of Year 2005
C25
-C31
Alk
ane
Mas
s (%
)
FALL
0 20 40 60 80
100
308
309
310
311
312
313
314
315
316
317
318
319
Day of 2005
C25
-C31
Alk
ane
Mas
s (%
)
Biogenic Wax Anthropogenic
Biogenic Wax Anthropogenic
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0 5*10^5 10^6 1.5*10^6
Relative Abundance 17alphah21betah.hopane
0 100000 200000 300000 400000 500000
Relative Abundance28nor17betah.hopane
0 100000 200000 300000 400000
210 212
214 216
218 220
Day
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Day
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N
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)-hopane N SS
DO
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210 212
214 216
218 220
Day of Y
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210
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220
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Retene NAmbient
40Filtered30
Particle 20
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Meat Cooking
Burning
Rel
ativ
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2000
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210 212 214 216 218 220
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Day of Year 2005
215
216
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218
220
215
216
210 212 214 216 218 220
Day of Year 2005 S
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Pinonaldehyde NAmbient 10
86
FilteredParticle 4
210 212 214 216 218 220 S
Anthropogenic Secondary
Biogenic Secondary
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Phthalic Acid N
5040
3020
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210 212 214 216 218 220
215Day of Year 2005
216
210
2
112
11
211
2
12
212
2
132
13
213
Day of Year 2005
214
215
216
214
217
217
2
17
218
218
2
192
19
219
2
202
20
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4030
2010
EW
5-pentyl-dihydro-2(3H)-furanone
2 W E
S
DOY> 210
212
218
220
214
215
216
210 212 214 216 218 220
Day of Year 2005 S
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ctorizatio
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esults
F ac to r C on tribu tions to P a ram e te r C oncen tra tions (% )
140
120
100
80
60
40
20 0
-20
-40
d in o n y lp h th a la te p e n o xa l in e
h e xa d e ca n o ic .a c id -m e th y le s te r d io c ty lp h th a la te
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3 -m e th y lp h th a l ic .a c id 4 -m e th y lp h th a l ic .a c id
p h th a l ic .a c id d im e th y l iso b e n zo fu ra n d io n e
5 -m e th y l-2 -n itro p h e n o l d ih yd ro -5 -e th y l-2 (3 H )fu ra n o n e
d o d e ca n e d io n e d -te tra d e c a la c to n e
d io xa sp iro n o n a n e d io n e u n d e ca n e d io n e
b u ty lb e n ze n e su lfo n a m id e o c ta d e ca n o n e
d e h yd ro a b ie tic .a c id -m e th y le s te r c h lo ro p h o s p h a te p ro p a n o l
2 -m e th y la n th ra ce n e n o n a d e ca n e
iso p ro p y l-d im e th y lp h e n a n th re n e te tra co s a n e
d ip h e n y l .e th a n e d io n e 2 -m e th y lo c ta d e ca n e
n o rh o p a n eh o p a n e
4 -m e th y lo c ta d e ca n e 3 -m e th y lo c ta d e ca n e 2 -m e th y lo c ta d e ca n e
la te .5 7 a n th ra c e n e
m o n o p a lm itin n o n a d e cy lcyc lo h e xa n e
n o n a d e ca n e m o n o s te a rin
o c ta d e c y lcy c lo h e x a n e c y c lo p e n ta (c d )p y re n e
e ico sy lcyc lo h e xa n e h e x a d e c a n o ic .a c id o c ta d e c a n o ic .a c id o c ta d e c a n e n itri le
h e xa d e c a n e n itri le d im e th o xyd ip h e n y l.e th a n o n e
e u p a to rio ch ro m e n e m e th y ld ia m a n ta n e
d -ca d in e n e e n ce ca l in
va n i l l in tria c o n ta n e
o c ta co s a n e h e n tria c o n ta n e
n o n a co sa n e h e xa co sa n e
h e p ta co s a n e m e th y lo xa a d a m a n ta n e
m e th o xyp y rid in e p e l le tie r in e
p -cym e n e n e d -3 -ca re n e
p e n ty lc yc lo h e x a n o n e a -p h e l la n d re n e
m e th o xyp h e n y lm e th y le n e .b e n ze n a m in e d io xa sp iro u n d e ca n o n e
l im o n e n e m e th y l fu ra n o n e
s a b in a .k e to n e d i.te rt.b u ty ln i tro p h e n o l
n o ra b ie ta .4 .8 .1 1 .1 3 .te tra e n e d ip h e n y la m in e
n o ra b ie ta te tra e n e -m ix tu re 7 -o xo d e h yd ro a b ie tic .a c id -m e th y le s te r
2 -m e th y lp y re n e
SO
AR
Su
mm
er Org
anic A
eroso
l Facto
r Pro
files
SOA1
SOA2
SOA3
RegionalPrimaryAnthro
LocalVehicle FoodC
ooking BioParticle+M
ixed BioSem
ivolatile Biom
assBurning Residual
~ -0.0012
□ 0 .0012 - 0.0018 0 0 .001B - 0.0027
□ 0 .0027. 0.0040
□ 0 .0040 - 0.0060
□ 0 .0060 - 0.0090 ■ 0,0090 - 0,0136 ■ o,orn; _ 0,0203
□ 0,0203 - 0,0305 ■ 0 ,0305 - 0 ,0458
■ 0 ,0458 - 0 ,0686
■ 0 ,0686 - o,i.o 3o ■ > 0 ,1030
SOA3SOA2SOA1NNN 20 2525
2015 20151510
10105 5WEW WE E
5
SSS
FoodCookingLocalVehicleRegionalPrimaryAnthroNNN 20 158
15 6 10410
525W WE EWE
SSS
BiomassBurningBioSemivolatileBioParticle+MixedN 15N15N
54 10 103
52 51
EWEWEW
SSSResidual N
10N
86 888000 k k kmmm4
2W RRRiiivvveeerrrsssiiidddeeeLLLooosss AAAnnngggeeellleeesssE
111333555 k k kmmmS
SSSaaannn DDDiiieeegggooo
SOA1 SOA2 SOA3 N N N20 2525
2015 20151510
1010 5 5 E WW E W E
5
SOAR Summer Organic Aerosol
S S S
RegionalPrimaryAnthro LocalVehicle FoodCooking SourcesN N N20 15
815 6 10
410525
W E W EE W
SS S
BioSemivolatile BiomassBurningBioParticle+Mixed N
5 N 15 N 15
4 10 103 52 51
EE WWEW
S SS Residual N
N 108
6 80 km42
W RiversideE Los Angeles
135 kmS
San Diego
■
l ~~ ■
D
i ~'
l ~ ', I
■
■
D
■
; ~ ! ! i
! I I I
~ ; .! ! ! ~ I
7
Po
sitive
Matrix
Fa
ctorizatio
n(P
MF
)R
esults
F a c to r C o n trib u tio n s to P a ra m e te r C o n c e n tra tio n s (%
nitrop he ny lben z e nam ine oc tad ec ano ic .a c id
o le ic .a c id te trad ec ano ic .a c id
p e lle tie r ine he x ad ec ano ic .a c id
do dec an ed ione 4 -n itro phe no l
ben z y lbe nz o a te d iox as p iro un dec an one
he n tr iac on tane n ona na l
m o no s te a r in p h th a lim id e
o c ta de c an en itr ile he x a de c an en itr ile
un dec an ed ione x a n th one
pen tad ec ene na ph tho fu ra nd ione
m o no pa lm itin d -oc ta lac tone
d ih y d ro - 5 -e thy l-2 ( 3H ) fu ran one d -no na lac tone
r im u ene c y c lope n ta (d e f)p he nan th r en one
3 - m e thy lph tha lic .ac id s ab ina .k e ton e
ph tha lic .a c id 1 ,8 -n ap h th a lic anh y d r ide
d ih y d ro - 5 -d ode c y l-2 ( 3H ) fu ran one m e thy lfu ran one
be nz o ic .a c id a n th raq u in one
c um in ic .a ldeh y d e no nad ec ane
4 -m e th y loc tad ec ane 2 -m e th y loc tad ec ane
hen e ic os ane te tr ade c y lc y c loh ex ane
pe n tade c y lc y c loh ex ane 3 -m e th y loc tad ec ane
h op ane n o rh op ane
c y c lop en ta (c d ) py r ene ac e ph ena n th ry lene
la te .57 eup a to r io c h r om en e
oc tade c y lc y c loh ex ane e ic o s y lc y c loh ex ane
n ona de c y lc y c loh ex ane d io c ty lph tha la te
c h ry s ene he p tade c y lc y c loh ex ane
a n th rac ene m e th ox y ph en y lm e th y le ne .ben z e nam in e
a - phe lla nd r ene e thy lm e th y lfu ran
g - te r p in ene m e thy lox aad am an tan e
d -do de c a lac tone no rab ie ta .4 .8 .1 1 .1 3 .te tra ene
is op ro py l.d im e th y lp he nan th r ene re tene
no r ab ie ta te tr aen e - m ix tu r e d eh y d r oa b ie tic .a c id -m e th y le s te r
7 -o x od eh y d r oa b ie tic .a c id -m e th y le s te r d im e thy lbu ty lp he ny l.ben z e ned iam in e
p inon a ld eh y de
SO
AR
Fall O
rgan
ic Aero
sol F
actor P
rofiles
-60.0
-40.0
-20.0
0.0
20.0
40.0
60.0
80.0
100.0
120.0
140.0
160.0
SOA+FoodC
ooking1 SO
A+FoodCooking2
RegionalPrimaryAnthro
LocalVehicle BioSem
ivolatile Biom
assBurning Residual
V \/ / \.
,,-, '> \. I ..._ -,; I
'- I--.. ~ I ,; - -I....._ ...._ I
- -'
I
- - L
I - I- '
I / ' I '\ .,..,....
/ \
I
' > I I -<
-7\--l\--f~=-= I \ ,..- "\ I ~
\ /,.... ( y..
.,., .... \ '/-....._1 ) '- I I-~ \
'7,
~ 0 - 0.0012
□ 0.0012 - 0.0018
□ 0 .0018 - 0 .0027
□ 0.0027 - 0.0040
□ 0.0040 - 0.0060
□ 0.0060 - 0.0090
■ 0.0090 - 0.0136
■ 0.0136 - 0.0203
□ 0 .0203 - 0 .0305
■ 0 .0305 - 0 .0458
■ 0 .0458 - 0.0686
■ 0 .0686 - 0 .1030
■ > 0 .1030
SOA+FoodCooking1 SOA+FoodCooking2 RegionalPrimaryAnthro10N N N 25108 8 20
6 156104 4
2 2E WW E W E
5
S S S
BioSemivolatileLocalVehicle BiomassBurningNN N
88 1566 104
224
5
W E WWE E
SSSaaannn DDDiiieeegggooo
S S S
ResidualN
64 N
2
W E 888000 kkkmmm
LLLooosss AAAnnngggeeellleeesss RRRiiivvveeerrrsssiiidddeee
S
111333555 kkkmmm
SOA+FoodCooking1 SOA+FoodCooking2 RegionalPrimaryAnthro N 10 N N 25
10
8 8 206 156
104 42 2
E WW E W E5 SOAR Fall
Organic S S S Aerosol
LocalVehicle BioSemivolatile BiomassBurningN N N
88 15 Sources66 104
2 2 4
5
W E WE W E
San Diego
S S S
ResidualN
6 4 N
2
W E 80 km
Los Angeles Riverside
S
135 km
□ □ ■
■ ■ □ ■
□ ■ ■
■ □ ■
□ ■ □ ■
1------·
Org
anic
Aer
osol
(ug
m-3
)O
rgan
icA
eros
ol(u
gm
-3)
Fri. Sat. Sun. Mon. Tues. Wed. Thur. Fri. Sat. Sun. Mon.30
AAMSMS OOrrggaanniiccss
20
10
0210 211 212 213 214 215 216 217 218 219 220 221
Day of Year 2005 (PST)
SSOOA1A1 RReeggiioonnaallPPrriimmaarryyAAnntthhrroo BBiiooPPaarrttiiccllee++MMiixxeeddSSOOA2A2 LLooccaallVVeehhiiccllee BBiiooSSeemmiivvoollaattiilleeSSOOA3A3 FFooooddCCooookkiinngg BBiioommaassssBuBurrnniinngg
RReessiidduuaall
Tues. Wed. Thur. Fri. Sat. Sun. Mon.Mon.Sun.Fri. Sat.
AAMMSS OOrrggaanniiccss20
15
10
5
0308 309 310 311 312 313 314 315 316 317 318 319
Day of Year 2005 (pst)
SSOOAA+F+FooooddCCooookkiinngg11 BBiiooSSeemmiivvoollaattiilleeSSOOAA+F+FooooddCCooookkiinngg22 BBiioommaassssBuBurrnniinnggRReeggiioonnaallPPrriimmaarryyAAnntthhrroo RReessiidduuaallLLooccaallVVeehhiiccllee
SOAR Summer
SOAR Fall
Org
anic
Aer
osol
(ug
m-3
) O
rgan
ic A
eros
ol (
ug m
-3)
Fri. Sat. Sun. Mon. Tues. Wed. Thur. Fri. Sat. Sun. Mon. 30
AMS Organics
20
10
0 210 211 212 213 214 215 216 217 218 219 220 221
Day of Year 2005 (PST)
SOA1 RegionalPrimaryAnthro BioParticle+Mixed SOA2 LocalVehicle BioSemivolatile SOA3 FoodCooking BiomassBurning
Residual
Fri. Sat. Sun. Mon. Tues. Wed. Thur. Fri. Sat. Sun. Mon.
AMS Organics 20
15
10
5
0 308 309 310 311 312 313 314 315 316 317 318 319
Day of Year 2005 (pst)
SOA+FoodCooking1 BioSemivolatile SOA+FoodCooking2 BiomassBurning RegionalPrimaryAnthro Residual LocalVehicle
■ □
■
□ □ ■
□ ■ ■
□ ■ □ ■
2:00
4:
8:00
00
:
2:00
4:
8::00
00
13.6
13.5
14.5
16.5
20.220.2
21.3
19.8
13.1
10.0
15.0
20.8
--OOrgrgaanniiccss ( (µµgg mm--33)) NONO3322-- ++SSOO44 NHNH44
30.6 26.3 µg m-3
22.9 28.7
33.8 32.9
40.242.1
AMS Total Organic Aerosol = 10.0 - 20.8 µg m-3
44.6
20.6
0:00
00
6:00
00
10:0012:00
14:00
16
18:00
20:
22:00
26.3
36.3 44.6
20.6
0:00 2:00
4:00
6:00
8:00
10:0012:00
14:00
16:00
18:00
20:00
22:00
13.6
13.5
14.5
16.5
20.220.2
21.3
19.8
13.1
10.0
15.0 26.3
20.8
36.3
-Organics (µg m-3) NO3 2- +SO4 NH4
30.6 26.3 µg m-3
TAG-defined Organic Aerosol Sources 22.9 28.7
33.8 32.9
42.1 40.2
AMS Total Organic Aerosol = 10.0 - 20.8 µg m-3
SOAR Summer
13.5
13.6 µg m-3
14.5
16.5
20.8
20.220.2
21.3
19.8
13.1
10.0
15.0
0:00
00
6:00
00
10:0012:00
14:00
16:
18:00
20:
22 00
AMS Total Organic Aerosol = 10.0 - 20.8 µg m-3
SOA1SOA2SOA3
RegionalPrimaryAnthroLocalVehicleFoodCooking
BioParticle+MixedBioSemivolatileBiomassBurningResidual
13.5
13.6 µg m-3
14.5
16.5
20.8
20.220.2
21.3
19.8
13.1
10.0
15.0
0:00 2:00
4:00
6:00
8:00
10:0012:00
14:00
16:00
18:00
20:00
22:00
AMS Total Organic Aerosol = 10.0 - 20.8 µg m-3
SOA1 SOA2 SOA3
RegionalPrimaryAnthro LocalVehicle FoodCooking
BioParticle+Mixed BioSemivolatile BiomassBurning Residual
ChlorideChlorideChloride
■ □
■
■ ■ □ ■
■ □ ■
2:00
4:
8:00
00
9.9
11.3
10.3
11.6
10.5
10.26.0
6.2
8.2
10.0
10.8
10.3
2:00
4:
8:00
00
9.9
11.3
10.3
11.6
10.5
10.26.0
6.2
8.2
10.0
10.8
10.3
2:00
4:
8:00
00
2233..11 µµgg mm--332244..4424.4 23.1 µg m-3
SOAR Fall
TAG-defined Organic Aerosol Sources
Organics (µg m-3)SO4
2-NO3
-
NH4+
Chloride
AMS Total Organic Aerosol = 6.0 – 11.6 µg m-3
26.0
24.7
27.7
25.4
24.515.0
16.0
21.5
25.3
25.4
0:00
00
6:00
00
10:0012:00
14:00
16:
18:00
20:
22:00
Organics (µg m-3)SO4
2-NO3
-
NH4+
ChlorideOrganics (µg m-3) SO4
2-NO3
-
NH4 +
Chloride
AMS Total Organic Aerosol = 6.0 – 11.6 µg m-3
26.0
24.7
27.7
25.4
24.515.0
16.0
21.5
25.3
25.4
0:00
00
6:00
00
10:0012:00
14:00
16:
18:00
20:
22:00
26.0
24.7
27.7
25.4
24.515.0
16.0
21.5
25.3
25.4
0:00 2:00
4:00
6:00
8:00
10:0012:00
14:00
16:00
18:00
20:00
22:00
9.9
11.3
10.3
11.6
10.5
10.26.0
6.2
8.2
10.0
10.8
10.3 9.9
11.3
10.3
11.6
10.5
10.26.0
6.2
8.2
10.0
10.8
10.3
AMS Total Organic Aerosol = 6.0 – 11.6 µg m-3
11.3
9.9 µg m-3
10.3
11.6
10.5
10.26.0
6.2
8.2
10.0
10.8
10.3
0:00
00
6:00
00
10:0012:00
14:00
16:
18:00
20:
22:00
SOA+FoodCooking1SOA+FoodCooking2RegionalPrimaryAnthroLocalVehicle
BioSemivolatileBiomassBurningResidual
AMS Total Organic Aerosol = 6.0 – 11.6 µg m-3
11.3
9.9 µg m-3
10.3
11.6
10.5
10.26.0
6.2
8.2
10.0
10.8
10.3
0:00 2:00
4:00
6:00
8:00
10:0012:00
14:00
16:00
18:00
20:00
22:00
SOA+FoodCooking1 SOA+FoodCooking2 RegionalPrimaryAnthro LocalVehicle
BioSemivolatile BiomassBurning Residual
Average Source Concentrations and Contributions to Total OA during SOAR 2005.
SUMMER FALL Average
Concentratio n (ug m-3)
Contribution to Total
Organics (%)
Average Concentratio
n (ug m-3)
Contribution to Total
Organics (%) SOA1 1.61 9.9 SOA+FoodCooking1 1.26 13.0 SOA2 3.06 18.9 SOA+FoodCooking2 5.47 56.3 SOA3 2.92 18.0 RegPrimAnthro 1.46 15.0
RegPrimAnthro 2.43 15.0 LocalVehicle 0.11 1.1 LocalVehicle 0.57 3.5 BioSemivolatile 0.18 1.9 FoodCooking 1.01 6.2 BiomassBurning 0.91 9.4
BioParticle+Mixed 1.10 6.8 Residual 0.33 3.4 BioSemivolatile 2.18 13.5
���
AMS O:C ~ TAG Compounds Measured during SOAR 2005 OOA1 (0.9) 300 Identified Hourly (~10-20% of organic mass)
Increasing oxidation � increasing measurement difficulty
OOA2 (0.55)
BBOA (0.35)
HOA (0.08)
0
0.1
0.2
0.3
0.4
0.5
0.6
15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0
Retention Time (min)
O:C
0
50
100
150
200
250
300
350
GC
Ove
n T
empe
ratu
re (
o C
)
C26
O0
O1
O2
O3
O4 C7
C9
C21 C17
C11
C14
Aiken et al., submitted ES&T Williams et al., in prep
60 ■ other ■ sum(halogens) 11 PANs ■ aromatics
50 E'd:I MVK+MACR □ i soprene □ monoterpenes □ formaldehyde
40 ~ acetaldehyde ■ formic acid ~ acetic acid ■ ethanol
30 ~ methanol □ acetone I'd:! butane ■ propane
20 ~ ethane ■ oc aerosol
(J ·-C n:s 10 O') a... 0
0
Total Observed Organic Carbon (TOOC)Organic aerosol = 3-17%
Total Observed Organic Carbon (TOOC) Organic aerosol = 3-17%
[Heald et al., ACP 2008]
05*
10^5
10^6
1.5*
10^6
02*
10^6
4*10
^66*
10^6
8*10
^60
5*10
^510
^62*
10^6
3*10
^6
TAG Particle+Gas Ambient Measurements
02*
10^5
4*10
^56*
10^5
8*10
^510
^60
5*10
^510
^61.
5*10
^62*
10^6
02*
10^6
6*10
^610
^71.
4*10
^7
02*
10^5
6*10
^510
^60
10^6
2*10
^63*
10^6
4*10
^60
2*10
^66*
10^6
10^7
210 212 214 216 218 220210 212 214 216 218 220210 212 214 216 218 220
210 212 214 216 218 220 210 212 214 216 218 220210 212 214 216 218 220
210 212 214 216 218 220210 212 214 216 218 220210 212 214 216 218 220
pent
acos
ane
nona
deca
ne
trid
ecan
e
0 5*
10^5
10
^6
1.5*
10^6
0
2*10
^6
4*10
^6
6*10
^6
8*10
^6
0 5*
10^5
10
^6
2*10
^6
3*10
^6
DOY>
TAG Particle+Gas Ambient Measurements C13 Alkane C15 Alkane C17 Alkane
nona
cosa
ne
tric
osan
e he
ptad
ecan
e
0 2*
10^5
4*
10^5
6*
10^5
8*
10^5
10
^6
0 5*
10^5
10
^6
1.5*
10^6
2*
10^6
0
2*10
^6
6*10
^6
10^7
1.
4*10
^7
hept
acos
ane
hene
icos
ane
pent
adec
ane
0 2*
10^5
6*
10^5
10
^6
0 10
^6
2*10
^6
3*10
^6
4*10
^6
0 2*
10^6
6*
10^6
10
^7
Particle+Gas Gas 210 212 214 216 218 220 210 212 214 216 218 220 210 212 214 216 218 220
Day of Year 2005 Day of Year 2005 Day of Year 2005
C19 Alkane C23 AlkaneC21
Alkane
210 212 214 216 218 220 210 212 214 216 218 220210 212 214 216 218 220
Day of Year 2005 Day of Year 2005Day of Year 2005
C27 Alkane C29 AlkaneC25 Alkane
214
215
216
210
212
214
215
216
210 212 214 216 218 220 210 212 214 216 218 220 210 212 214 216 218 220
Day of Year 2005 Day of Year 2005Day of Year 2005
214
215
216
211
213
217
218
219
220
210
211
212
213
217
218
219
220
210
211
212
213
217
218
219
220 DOY>DOY>
Williams et al in prep
.. ■
■ ... ..
•■ , ..
'II .. .. . -■
. ■ • ■ - - ---...
. , .. . , . , ,
■ .
' I . .
' ~ I/
••
- ... -- ... -
• - ... -- ... -- ... -- ... -- ... -
,■ ,
Gas-Particle Partitioning from TAGAmbient Measurements by Compound Class
Gas-Particle Partitioning from TAG Ambient Measurements by Compound Class
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31
Number of Carbon
Fra
ctio
n in
Par
ticle
Pha
se (
acco
rdin
gto
TA
G c
olle
ctio
n)
Alkanes
Alkanoic Acids Dihydro-2(3H)-Furanones
Cyclohexanes
PAHs
Phthalates Alkanones
___ Fall …... Summer
Williams et al in prep
Summary • Achieved hourly speciated organic aerosol measurements
during SOAR campaign for >300 compounds • Differentiated biogenic and anthropogenic contributions of
primary and secondary organic aerosol in Riverside, and quantified large diurnal cycles in source contributions
• Secondary compounds, many of which are semi-volatile, dominate the organic aerosol in Riverside in afternoon
• TAG measurements observe ambient gas-particle partitioning and hence offer insight to the formation of SOA
Future • Analyzing 2007 BEARPEX data from Blodgett Forest • Developing multi-dimensional TAG (2D-TAG) for improved
compound separation • Developing Semi-Volatile TAG (SV-TAG) for simultaneous
quantitative measurements of gas and particle composition • Planning additional urban and rural field measurements
Funding DOE STTR DOE SBIR
2D-TAG
TWO-DIMENSIONAL CHROMATOGRAPHY OF ATMOSPHERIC AEROSOLS: A NEW IN-SITU INSTRUMENT
Allen H. Goldstein, Brent J. Williams University of California, Berkeley
Susanne V. Hering, Nathan M. Kreisberg Aerosol Dynamics Inc.
Tadeusz Górecki, Ognjen Panic University of Waterloo
-Hourly, in-situ characterization of organic markercompounds in ambient aerosols
TAG (1D) Thermal desorption Aerosol GC -Hourly, in-situ characterization of organic marker compounds in ambient aerosols (Williams et al AS&T 2006)
2D-TAG 2-Dimensional Thermal desorption Aerosol GC -Vastly increase number of separated compounds -Classify compounds by chemical family and size
(Goldstein et al J Chrom A 2008)
- -
1-D Chromatography Separation limited by column capacity
Difficult separating highly complex samples
First dimension elution
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column phases Se
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First dimension elution (e.g. boiling point separation)
1D vs 2D Separations with TAG EPA Standard Method 8270
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2 6 0 2 8 0 3 0 0 3 2 0
x 1 0 6
1D 1 5 0
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Separation of Diesel Fuel Using 2D-TAG VS 1D-TAG (note compound class structures)
di-aromatics
mono-aromatics
alkanes
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2000
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2D-TAG-FID Berkeley Air
90 minute sample
12:00
Boiling Point
Polarity
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Polarity
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Polarity
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Polarity
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Summary • 2D TAG-FID is now operational • Optimizing chromatography • Building 2D-TAG with TOF-MS (DOE STTR) • 2nd dimension aids identification and quantification • Goal – hourly quantitative timelines for extensive
range of marker compounds in ambient aerosols • Data analysis presents many challenges and also
opportunities to consider classes of compounds