preliminary results from pie 2005 the pan intercomparison exercise f. flocke, g. tyndall, e. apel...
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PRELIMINARY RESULTSfrom
PIE 2005the PAN Intercomparison Exercise
F. Flocke, G. Tyndall, E. Apel (NCAR)
E. Williams (NOAA)
PIE 2005
• 6/28-7/8/2005
• Enchanted Mesa
• eight different instruments
• from Canada, Germany, Japan, the UK, and the US
• five different methods
• ambient and standards measurements
results arePRELIMINARY
Instruments• Hiroshi Tanimoto, NIES, Japan; GC/MS
• Graham Mills, UEA, UK, GC/ECD
• Stefan Gilge, DWD, Germany, GC/ECD
• Bernhard Rappenglueck and Rainer Schmitt, U. Houston and Metcon, Germany, GC/ECD
• Jason O’Brien, Environment Canada, GC/PDD
• Ron Cohen, Paul Wooldridge, Anne Perring, UCBerkeley, TD-LIF
• Jim Roberts, NOAA, GC/ECD
• Aaron Swanson, NCAR and Saewung Kim, GaTech, CIMS
• (Frank Flocke, NCAR, Dual-GC/ECD)
Other Instruments
• Meteorological parameters (NOAA)
• NO, NO2, O3 (NOAA)
• NOy reference instrument in referee trailer (NCAR)
EnchantedMesa
Internet Access, email
The forbiddenzone
Flow: 12~20 slpm
GC5
standardsambient
Photo of site
Photos of setup
UEA GC/ECD
• Restek MXT-200 Column
• 0.53 ID, 10 m, 1.0µ film
• 22 sccm
• 17 ºC isothermal
• cycle time 10 minutes
• PAN, PPN
Env. CAN GC/PDD
• Restek MXT-200 Column
• 0.53 ID, 8 m, 1.0µ film
• 35 sccm
• 15 ºC isothermal
• cycle time 10 minutes
• PAN, PPN
NOAA GC/ECD
• Restek Rtx-200 Column
• 0.53 ID, 7.5 m, 1.0µ film
• 10 sccm
• 15 ºC isothermal
• cycle time 5 minutes
• PAN, PPN, APAN, MPAN, PiBN
NIES GC/MS
• DB-1 MS Column
• 0.25 ID, 10 m, 0.25µ film
• 2 sccm
• cycle time 10 minutes
• PAN, PPN, APAN, MPAN, PiBN, PnBN
UH/Metcon GC/ECDDWD GC/ECD
• DB1/DB-5 Column combination• 0.53 ID, ~10 m total• 20 sccm• ~15 ºC isothermal• PAN, PPN• cycle time 10 minutes• DWD GC has modified flow control (PAN only)
UC Berkeley TD-LIF
• measures NO2 by LIF
• has 3 thermal decomposition stages held at ~150, 300 and 550 degrees decomposing all PANs, ANs, “NOy” into NO2
• cycle time 10 seconds
• measures the sum of all PANs
NCAR/GaTech CIGAR
• measures PANs by CIMS
• PAN, PPN, PBN, APAN, MPAN, PBzN, MoPAN, PPeN, ...
• cycle time 2 seconds
• scans should show additional PANs unless they are very sticky
NCAR 2 Channel GC/ECD(“reference” instrument)
• 2 RTX-200 Columns
• 7.5m, 0.53 ID, 1.0µ film
• 20 sccm
• 20 ºC isothermal
• cycle time 3 minutes
• PAN, PPN, APAN, MPAN, PiBN
Measurements
• all measurements from common manifold
• ambient air
• PAN and PPN standards in dry zero-air from manifold
• PAN and PPN standards in humidified zero air
• i-Propyl nitrate (interferent) in zero-air
PRELIMINARY
Ambient Measurements
6/30/05 trace
3000
2000
1000
0
(ppt
v)
00:006/30/2005
06:00 12:00 18:00 00:007/1/2005
06:00
dat
Hou_PAN MOHP_PAN NIES_PAN NOAA_PAN Ref_PANppt UEA_PAN CIMS_PAN_average EnvCAN_PAN
6/30/05 trace
3000
2000
1000
0
(ppt
v)
00:006/30/2005
06:00 12:00 18:00 00:007/1/2005
06:00
dat
Hou_PAN LIF_PNs MOHP_PAN NIES_PAN NOAA_PAN Ref_PANppt UEA_PAN CIMS_PAN_average EnvCAN_PAN
7/4/05 trace2500
2000
1500
1000
500
0
(ppt
v)
00:007/4/2005
12:00 00:007/5/2005
12:00 00:007/6/2005
dat
Hou_PAN MOHP_PAN NIES_PAN NOAA_PAN Ref_PANppt UEA_PAN CIMS_PAN_average EnvCAN_PAN
7/4/05 trace2500
2000
1500
1000
500
0
(ppt
v)
00:007/4/2005
12:00 00:007/5/2005
12:00 00:007/6/2005
dat
Hou_PAN LIF_PNs MOHP_PAN NIES_PAN NOAA_PAN Ref_PANppt UEA_PAN CIMS_PAN_average EnvCAN_PAN
All ambient data2000
1500
1000
500
0
PA
N (
pp
tv)
2000150010005000PAN ref (pptv) ambient data
NIES_PANa MOHP_PANa Env_CAN_PANa NOAA_PANa UEA_PANa Hou_PANa CIMS_PAN_Averagea 1:1 line
All ambient data2000
1500
1000
500
0
PA
N (
pp
tv)
2000150010005000PAN ref (pptv) ambient data
NIES_PANa MOHP_PANa Env_CAN_PANa NOAA_PANa UEA_PANa Hou_PANa CIMS_PAN_Averagea 1:1 line +/-25%
All ambient data
600
400
200
0
PA
N (p
ptv)
6004002000PAN ref (pptv) ambient data
NIES_PANa MOHP_PANa Env_CAN_PANa NOAA_PANa UEA_PANa Hou_PANa CIMS_PAN_Averagea 1:1 line
All ambient data
600
400
200
0
PA
N (p
ptv)
6004002000PAN ref (pptv) ambient data
NIES_PANa MOHP_PANa Env_CAN_PANa NOAA_PANa UEA_PANa Hou_PANa CIMS_PAN_Averagea 1:1 line +/- 25%
i-Propyl nitrate
2500
2000
1500
1000
500
0
14:007/3/2005
14:30 15:00 15:30 16:00
dat
Hou_PAN LIF_PNs MOHP_PAN NIES_PAN NOAA_PAN Ref_PANppt UEA_PAN CIMS_PAN_average EnvCAN_PAN
PPN ambient
500
400
300
200
100
0
12:006/28/2005
00:006/29/2005
12:00 00:006/30/2005
12:00
dat
Hou_PPN NIES_PPN NOAA_PPN Ref_PPNppt UEA_PPN CIMS_PPN_average EnvCAN_PPN
PPN ambient
300
200
100
0
00:007/4/2005
12:00 00:007/5/2005
12:00 00:007/6/2005
dat
Hou_PPN NIES_PPN NOAA_PPN Ref_PPNppt UEA_PPN CIMS_PPN_average EnvCAN_PPN
PPN ambient
200
150
100
50
0
09:007/5/2005
12:00 15:00 18:00 21:00 00:007/6/2005
dat
Hou_PPN NIES_PPN NOAA_PPN Ref_PPNppt UEA_PPN CIMS_PPN_average EnvCAN_PPN
Standards2000
1500
1000
500
0
PA
N (
pp
tv)
2000150010005000PAN ref (pptv) DRY Standards only
NIES_PANa MOHP_PANa Env_CAN_PANa NOAA_PANa UEA_PANa Hou_PANa CIMS_PAN_Averagea 1:1 line
Standards2000
1500
1000
500
0
PA
N (
pp
tv)
2000150010005000PAN ref (pptv) MED Standards only
NIES_PANa MOHP_PANa Env_CAN_PANa NOAA_PANa UEA_PANa Hou_PANa CIMS_PAN_Averagea 1:1 line
Standards2000
1500
1000
500
0
PA
N (
pptv
)
2000150010005000PAN ref (pptv) WET Standards only
NIES_PANa MOHP_PANa Env_CAN_PANa NOAA_PANa UEA_PANa Hou_PANa CIMS_PAN_Averagea 1:1 line
Standards
1500
1000
500
0
(pp
tv)
15:007/2/2005
16:00 17:00 18:00
dat
Hou_PAN LIF_PNs MOHP_PAN NIES_PAN NOAA_PAN Ref_PANppt UEA_PAN CIMS_PAN_average EnvCAN_PAN
Standards6000
5000
4000
3000
2000
1000
0
14:007/2/2005
15:00 16:00 17:00 18:00 19:00 20:00
dat
Hou_PPN NIES_PPN NOAA_PPN Ref_PPNppt UEA_PPN CIMS_PPN_average EnvCAN_PPN
PRELIMINARYPRELIMINARY
LIF and the sum of PANs
6/30 ambient trace
3000
2000
1000
0
06:006/30/2005
09:00 12:00 15:00 18:00 21:00
dat
LIF_PNs ref_PANs CIMS_PANs
7/1 ambient trace4000
3000
2000
1000
0
06:006/30/2005
12:00 18:00 00:007/1/2005
06:00 12:00 18:00
dat
LIF_PNs ref_PANs CIMS_PANs
7/5 ambient trace3500
3000
2500
2000
1500
1000
500
0
09:007/5/2005
12:00 15:00 18:00 21:00 00:007/6/2005
dat
LIF_PNs ref_PANs CIMS_PANs
Standard comparison with LIF
6000
5000
4000
3000
2000
1000
0
15:007/2/2005
16:00 17:00 18:00
dat
LIF_PNs ref_PANs CIMS_PANs
Conclusions (for now)• very good agreement for ambient PAN
measurements, considering it’s field data• acceptable agreement for ambient PPN
measurements (might improve)• LIF measures consistently higher than sum of
individual PANs (expected?)• extra PANs that GCs and CIMS miss?• no indication of LIF counting ANs as PANs• LIF NO2 background subtraction problem?• more work has to be done to produce final data
and merge measurements together• compare MPAN, APAN, PBN