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Organic Aerosol Components VAPOrganic Aerosol Components VAP for
Aerosol Mass Spectrometers
Qi Zhang
OA Components VAP• Goal: To represent the enormously complex atmospheric
OA system as lumped descriptions of a limited number of t th t b l t d t di ti tcomponents that may be related to distinct sources,
physicochemical properties, and atmospheric processes.
• Methodology : Multivariate statistical analysis of DOE ACRF and IOP aerosol mass spectrometer data.
• Assumption: An AMS organic aerosol data matrix is comprised of the linear combination of OA components p pwith constant profiles that have varying contributions across the dataset.
Aerosol Mass Spectrometer (AMS) SystemsLong term measurements (3 systems) –Aerosol Chemical Species
MonitorACSM
(mini-AMS)
Long term measurements (3 systems) Tropical Western Pacific in Darwin, AustraliaThe Southern Great Plains, OklahomaACRF MAOS mobile facilityMonitor
Quadrupole AMS
(mini AMS)
Q AMS
ACRF MAOS mobile facility
Intensive focused studies (IOP)Quadrupole AMSCompact Time-of-Flight AMS
Q-AMSc-ToF-AMS
Intensive, focused studies (IOP)• CARES: 3 HR-ToF-AMS (T0, T1, G1)• BNL-IOP
GVEX t l t 3
High Resolution Time-of-HR-ToF-AMS• GVEX: at least 3 • ASP previous G1 studies: NEAQS (2002),
MASE (2005), MAX-Mex (2006), MAX-Tex Flight AMS(2006), CHAPS (2007), and VOCALS
(2008)
3. 0
2. 5
2. 0
1. 5
Mas
s C
once
ntra
tion
(µg
m-3
)
Am m on ium 4 .8 ug /m 3Nitra te 5 .8Su lpha te 9 .4Organ ics 13.4Ch lo ride 0.15
M ex ic o C i ty 2/200 2
43 44
High time resolutionAMS Data
1. 0
0. 5
0. 0
Nitr
ate
Equi
vale
nt M
141201 0080604 020m /z (D alt ons )
SO+SO2
+
S+
SO3+
HSO3+
H2SO4+
57ACSM(mini-AMS)
High time resolution
1. Quantitative composition(mini AMS)
Q AMS15 - 30 min.
Q-AMSc-ToF-AMS
2. Size‐resolved composition
m/z 43C2H3O+HR-ToF-AMS
CHNO+C2H5N+
C3H7+
CH3N2+
2-5 min. (ground)5-30 s (airborne)
3. Elemental comp. (CnHmNpOzSw)
AMS Organic Mass Spectrum
ORGt×i
msmeasured = ca· msa + cb· msb + cc· msc + …
0.30
ORGt×i
t = 50 – 300 / dayi 200 1000
0 15
0.20
0.25
Inte
nsity
All
i = 200 - 1000 t×i = 1E4 – 3E5 /day
0 00
0.05
0.10
0.15
150200
250
Sign
al All
observations
0.00
050
100150
23:20:00 23:30:00
23:40:00 23:50:00 00:00:00 00:10:00 00:20:00
m/zSampling timet0t1
t2t3
......
multivariate
OA1, OA2, OA3, …analysis
Multivariate analysis methods:• Positive Matrix Factorization (PMF)Positive Matrix Factorization (PMF)• Tracer-based linear decomposition• Spectra based linear decomposition• Spectra-based linear decomposition
(chemical mass balance-style)Literature (applications to AMS data):• Zhang, Q. et al. (2005), Deconvolution and quantification of hydrocarbon-like
and oxygenated organic aerosols based on aerosol mass spectrometry, ES&T,and oxygenated organic aerosols based on aerosol mass spectrometry, ES&T, 39(13), 4938-4952
• Ulbrich, I., M. et al. (2009), Interpretation of Organic Components from Positive Matrix Factorization of Aerosol Mass Spectrometric Data, Atmos. Chem. Phys., 9, p y2891-2918.
• Ng, N. L. et al. (2010), Development of Real-Time Methods for the Estimation of Organic Components for Aerosol Mass Spectrometer Data, ES&T (submitted).
Modelers are using the OA component data derived from AMS field data.
9
6
Sulfate
8
6
(a) LV-OOA (low volatility, oxygenated OA) Sulfate 18
12
H/C=1.29; O/C=0.63; N/C=0.011OM/OC=1.96
CxHy+ CxHyO1
+ CxHyO2
+
+ + +
LV-OOAOA Components – Urban Case
10
6
3
0
e (µg/m3)
4
3
Nitra
0.2
Chlo
4
2
0(b) SV-OOA (semivolatile, oxygated OA)
m3 ) Nitrate
Chloride10
8
6
0H/C=1.40; O/C=0.38; N/C=0.004OM/OC=1.63
HyO1 +CxHyNp
+ CxHyOzNp
+
SV-OOA
5
0
6
3
2
1
ate (µg/m3)
C3
0.1
0.0
oride (µg/m3)
mpo
nent
s (µ
g/m
(c) NOA (nitrogen-enriched OA) C3H8N+ 12
6420
H/C=1.50; O/C=0.37; N/C=0.053OM/OC 1 69na
l
NOASeparation of different types of POA and SOA
9
6
4
2
0
0.2
0.1
0.0
3 H8 N
+ (µg/m3)
tion
of O
A c
om
( ) ( g )
+
9630
OM/OC=1.69
% o
f Tot
al S
ig
Op ypLow Volatility Oxygenated (LV-OOA) ~ Aged, regional SOA
Semi-volatile Oxygenated (SV-OOA) ~ Fresher semi-volatile SOA9
6
3
0.04
0.02
C6 H
10 O+(µg/m
3(d) COA (cooking-emission related OA)
Con
cent
rat
C6H10O+ 8
6420
H/C=1.58; O/C=0.18; N/C=0.004OM/OC=1.38
COASemi-volatile Oxygenated (SV-OOA) ~ Fresher, semi-volatile SOA
Nitrogen-enriched (NOA) ~ Amine type, likely SOA
H d b lik (HOA) T ffi b i POA09
6
3
0.00
3)
150
100
50
NO
x (ppbv
6
4
2
EC
(µg/m3
(e) HOA (hydrocarbon-like OA) ECNOx
010
8642
H/C=1.83; O/C=0.06; N/C=0.005OM/OC=1.24
HOAHydrocarbon-like (HOA) ~ Traffic, combustion POA
Cooking related (COA) ~ POA from cooking emissions
7/14 7/16 7/18 7/20 7/22 7/24 7/26 7/28 7/30 8/1 8/3
Date & Time (EST)
0 0
v)
0
3)
20092009120110100908070605040302010
m/z (amu)
20
Sun, Zhang et al., ACPD, 2010
OA Components – Rural / Remote Case
Chebogue Pt.Chebogue Pt.
2004 ICARTT
Nova Scotiabiogenically influenced
anthropogenically influenced.2004 ICARTT anthropogenically influenced.Zhang et al., in prep.
Separation of biogenic and anthropogenic SOASeparation of biogenic and anthropogenic SOA
CARES may be a good study case
Products:Ti i f OA (OA OA OA )
What Do We Get?
• Time series of OA comp. conc. (OAi; OAi ≈ OA mass)ACSM: 15 - 30 min.ToF-AMS: 2-5 min (surface) 15-30 s (airborne)
• Mass spectra of OA comp. distinct chemical properties, e.g., O/C, N/C, H/C, OM/OC
ToF AMS: 2 5 min (surface), 15 30 s (airborne)
g , , , ,• Typical OA comp.: HOA, OOA (SV-, LV-), BBOA, COA,
NOA...AAccuracy: • Propagated uncertainty for AMS data: < 30%, mainly due
to the collection efficiency (CE) correctionto the collection efficiency (CE) correction.• Uncertainties in OA components:
Can be evaluated: e.g., running the PMF algorithm from g , g g fdifferent random starting points; bootstrapping analysis (Ulbrich et al., 2009, ACP).
• Addressing the lifecycle processes of atmospheric OA
Applications of the OA Component VAP• Addressing the lifecycle processes of atmospheric OA.
• Temporal variations• Correlations with tracer compounds• Correlations with tracer compounds • size distributions…, integrated analysis
• Add i th di ti ti f OA• Addressing the radiative properties of OA. • Surrogates (e.g., O/C) for hygroscopicity and/or
volatilityvolatility.• Correlations and intercomparison with aerosol optical
and radiative measurementsand radiative measurements. • Validation and evaluations of models• Model development• Model development
1008404UrbanU b D i d
Global Distribution of SOA and POA840-4Urban DownwindRemote
12.3Pinnacle Park, NY
11.6
New York(Winter)
12.2
City, NY (Summer)
5.2
Manches(Winter)
14.3
ter, UK (Summer) 3.0
Edinburgh, UK16.3
TaunusGermany
4.2
MainzGermany 25.5
(W
in
5.3Chelmsford, UK
2.0
HyytialaFinland
Zurich,nter)
9.6
Switzerland
(Summ
14.7
burg
h, P
Adm
er)
2.3 JungfraujochSw
itzerland
7.0
Vanc
ouve
rC
anad
aPi
ttsh
16 2
4 4
2.1
Stor
m P
eak,
CO
V
80.0
Beijing
China
16.2 Tokyo,(W
inter)
13.2
Japa 11.07.910.72.98.59.52.826.812.819.1A
4.4
Bou
lder
, CO
an (Summ
er)
FukueJapan
OkinawaJapan
Cheju IslandKorea
ChebogueCanada
Off Coast New England, US
Thompson Farm, NH
Duke ForestNC
MexicoCity
Houston, TX
Riv
ersi
de, C
A
Jimenez et al., 2009
Global Distribution of SOA and POA
16
12
42%
Avg. OA = 7.3 µg/m3
18% 82%
Avg. OA = 4.9 µg/m3
10% 90%
Avg. OA = 2.7 µg/m3
Oxygenated OA
SemivolatileLow volatility
8
4
0
58%
nc. (g
m-3
)
Hydrocarbon-like OA16
12
8
4
Urban
Urban
Rural/RemoteDownwind
Mas
s C
on Hydrocarbon-like OA
Other, BB Fuel combustion
4
0
eijin
g, C
NTo
kyo,
JP
Sum
mer
)To
kyo,
JP
(Win
ter)
burg
h, P
A
exic
o C
ity
rsid
e, C
A
usto
n, T
X
ulde
r, C
Ok
City
, NY
mer
)k
City
, NY
nter
)ve
r, C
AN
urgh
, UK
hest
er,U
Km
mer
)es
ter,
UK
inte
r)M
ainz
, DE
uric
h, C
HS
umm
er)
uric
h, C
H(W
inte
r)st
NE
, US
rch
1, U
K
rch
2, U
K
unus
, DE
ue IS
, JP
wa
IS, J
P
S, K
orea
Pea
k, C
O
ores
t, N
C
Farm
, NH
PS
P, N
Y
otia
, CA
N
ytia
la, F
N
ujoc
h, C
H
OOA (l l SOA) d i OOA % i i h di f b
Be T (S T
Pitt
sb Me
Riv
er
Hou Bou
New
Yor
k(S
umN
ew Y
ork
(Win
Van
couv
Edi
nbM
anch
(Sum
Man
che
(Wi M Zu (S Zu (
Off
Coa
s
Tor
Tor
Tau
Fuku
Oki
naw
Che
ju I
Sto
rm P
Duk
e Fo
Thom
pson
F
Nov
a S
co Hyy
Jung
frau
• OOA (largely SOA) dominance, OOA % increase with distance from urban• HOA (largely urban POA) less significant at rural/remote, due to dilution
Zhang et al., 2009
Factor Analysis of AMS Organic Mass Spectramsmeasured = ca· msa + cb· msb + cc· msc + …
3.0
m-3
)
Ammonium 4 8 ug/m3
t = # of time stepsi = # of m/z p = # of comp.
ORGt×i = Ct×p × MSp×i + Et×i= tsa × msa + tsb × msb + tsc × msc + …
a a b b c c
43 442.5
2 0entra
tion
(µg
m Ammonium 4.8 ug/m3Nitrate 5.8Sulphate 9.4Organics 13.4Chl id 0 15
m/z (i) Component a Component cComponent b
SO+
SO2+
2.0
1.5
t Mas
s C
once Chloride 0.15
Mexico City 2/2002xtsa msa xtsc mscxtsb msb
Multivariate SO+
S+
SO3+
HSO3+
H2SO4+
57
1.0
0.5ate
Equi
vale
n
Time (t)
. . . + + …+
Multivariate Analysis
0.0
Nitr
a
1412010080604020
.
m/z (Daltons)t ~ 1,000si ~ 300