Air Pollution Research Using Chemical Mass …Air Pollution Research Using Chemical Ionization Mass...
Transcript of Air Pollution Research Using Chemical Mass …Air Pollution Research Using Chemical Ionization Mass...
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Air Pollution Research Using Chemical Ionization Mass Spectrometry (CIMS)Spectrometry (CIMS)
Jun Zheng, Ph.D.Jiangsu Key Laboratory of Atmospheric Environment
Monitoring and Pollution Control (AEMPC)Nanjing University of Information Science & Technology
Oct 26, 2012 Nanjing
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Soft IonizationHigh Sensitivityg yHigh SelectivityVersatilityVersatility
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Ion Chemistry: R(+/‐) + A P(+/‐) + BR(+/ ) + A P(+/ ) + B
Huey, L. G. (2007), Mass Spectrom. Rev., 26(2).Huey, L. G. (2007), Mass Spectrom. Rev., 26(2).
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Applications of CIMS in Atmospheric h dChemistry Study
Fi ld t t f• Field measurements: trace gases, free radicals…
• Laboratory experiments:– Kinetics
– Uptake coefficient
– Chamber simulations…
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1. Proton‐Transfer‐Reaction Mass ( )Spectrometry (PTR‐MS)
H3O+∙(H2O)n + R RH+ + H2O(n+1), (R = VOCs)3 ( 2 )n 2 (n+1), ( )
where n = 0, 1 and corresponding rate constants are k’0 and k’1, respectively.
[R] = [RH+] / (k’0[H3O+] + k’1[H3O+∙H2O])[R]t.
Ionicon Analytik Inc.
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PTR‐MS Field Measurements
Toluene Styrene C2‐BenzeneToluene Styrene C2-Benzene
C3‐Benzene Methanol AcetaldehydeC3-Benzene Methanol Acetaldehyde
Atmos. Chem. Phys. 2009, 9, 467‐481.
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VOCs Source Apportionments
VOC NOx
SO2 NOSO2 NOz
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PTR‐MS for HCHO Measurements
H3O+ + HCHO H+HCHO + H2O
Zheng et al., Atmos. Environ. 2012, Accepted
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Mobile VOCs Measurements
Case1: before vehicle control Case2: vehicle control before OlympicsCase3: Olympics Case4: between Olympics and Paralympics Case5: ParalympicsCase5: ParalympicsCase6: After vehicle controlCase7: National days
Atmos. Chem. Phys. 2009, 9, 8247‐8263.
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2. Ion Drift – CIMS2. Ion Drift CIMS
•Bipolar detector•Well‐controlled ion‐molecular reactionC bl f d l t i•Capable of declustering
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ID‐CIMSHNO3 Detection: SF6 + e‐ SF6‐
SF6‐ + SiF4 SiF5‐ + SF56 4 5 5SiF5‐ + HNO3 SiF5‐HNO3
N O Detection:N2O5 Detection: CF3I + e‐ I‐ + CF3I‐ + N2O5 NO3
‐ + INO2
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ID‐CIMS
Lei, W. F., R. Y. Zhang, X. X. Tie, and P. Hess (2004), Chemical characterization of ozone formation in the Houston‐Galveston area: A chemical transport model study, J. Geophys. Res., 109(D12), D12301, 10.1029/2003jd004219
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ID‐CIMS
HONO Detection: SF + e‐ SF ‐SF6 + e SF6SF6‐ + HONO HONOF‐ + SF5
(ppb
v)
30
40 ID-CIMSU. Miami LOPAP
ppbv)
HO
NO
(
10
20
HONO (p
CST
5/23 10:45 5/23 10:50 5/23 10:55 5/23 11:000
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ID‐CIMS2000
ptv)
1500
2000
pptv) 2009 In Houston, Texas
HO
NO
(p
500
1000
HONO (p
CST4/20 00 4/27 00 5/4 00 5/11 00 5/18 00 5/25 00 6/1 000
2009 In Shanghai, China
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3. Atmospheric Pressure IonizationID‐CIMS
Schematic diagram of the AP‐ID‐CIMS.
Chemical Scheme: NO - (HNO ) + H SO HSO - (HNO ) + HNO n = 0 1 2 Chemical Scheme: NO3 (HNO3)n + H2SO4 HSO4 (HNO3)n + HNO3, n = 0,1,2… Quantification: [H2SO4] = [HSO4
-HNO3] / (k∆t[NO3-HNO3])
By introducing a 4-in ID inlet for sampling, the wall losses can besignificantly decreased.
Well suited for the detection of ultra-trace atmospheric components, such asgaseous sulfuric acid (the detection limit as low as 0.01 ppt).
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API‐ID‐CIMS
2008 Beijing2008 Beijing
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API‐ID‐CIMSNucleation Events During CAREBeijing 2008
080717
4.E+04
5.E+04
6.E+04
(/cm
3 ) 2 .0E+06
2.5E+06
3.0E+06
H2 SO
4
N uc leation
H2SO4
Nucleation Events During CAREBeijing 2008
0.E+00
1.E+04
2.E+04
3.E+04
00 04 08 12 16 20 00T ime
N-
Nuc
(
0 .0E+00
5.0E+05
1.0E+06
1.5E+06
(/cm
3)
JT JT0([H2SO4 ] )a a ( RH )b b ( [NH3] )c c
a = 2.17 in Beijing, indicating 2 H2SO4 molecules were involved in the nucleation
JT JT ([H2SO4 ] 0
) (RH0
) ([NH 3]0
)
McGraw, R., and Zhang, R. Y., J. Chem. Phys., 128, 2008.
a 2.17 in Beijing, indicating 2 H2SO4 molecules were involved in the nucleation
Zheng, J. et al., Atmos. Chem. Phys., 11, 2011.
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4. High Resolution Time of Flight‐CIMS4. High Resolution Time of Flight CIMS
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HRToF‐ID‐CIMS
Aerodyne HRToF‐CIMS
O2+
CH5NH+
Amonia and Amines in Nanjing 2012
CH5N H
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AcknowledgementsAcknowledgements
• Prof Renyi ZhangProf. Renyi Zhang
• Prof. Mindong Chen
f i i Ch• Prof. Jianmin Chen
• Prof. Min Hu
• Prof. Yan Ma
• Prof Lin WangProf. Lin Wang
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Thank you for your attention!