PRELIMINARY RESULTS from PIE 2005 the PAN Intercomparison Exercise F. Flocke, G. Tyndall, E. Apel...

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