Transcript Folie 1 - Accent

Towards an improved European Infrastructure for reactive trace gas monitoring
within ACTRIS
Christian Plass-Duelmer, Stefan Reimann, S. Gilge, A. Werner, C. Hoerger, the ACTRIS Team
1
WP4: Trace gases networking: Volatile organic carbon and nitrogen oxides
EMEP
WMO/GAW
Data Quality Objective
Meas. Guidelines
CCL
WCC / QA-SAC
Qualtity Assurance
Data Reporting
AMOHA
FP5 project
ACTRIS-VOC/NOx Activities
Integration/Harmonization
Funding
2
Reactive Gases
Development of concepts, drafts,
dissemination, revisions in
ACTRIS NA4 Community
Work shop Ispra, Oct 2011,
Work shop Hohenpeißenberg, June 2012
Several bi-lateral meetings
ACTRIS-GAW Community
GAW VOC Expert Group, York, Sep 2012
WMO/GAW Meeting, Geneva, Feb 2013
ACTRIS-EMEP Community
EBAS Data workshop, Oslo, May 2012
EMEP TFMM , May 2011, May 2013
ACTRIS-AQUILA Community
Cooperation in method development,
Participate in RR and intercomparisons
3
MPI
UHEI
LGR
X
X
X
X
X
X
X
X
X
X
REG
GLOB
CONTR
WCC
WCC
X
X
X
X
X
X
X
X
GLOB
REG
GLOB
CONTR
CONTR
CONTR
CONTR
CONTR
GLOB
REG
GLOB
X
X
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X
X
X
X
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A
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A
A
X
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X
X
X
X
X
X
X
X
VOC EBAS
X
X
X
X
X
X
X
X
X
X
BVOC-RR
X
X
X
NMHC-RR
A
A
A
PTRMS
X
X
X
OVOC
X
X
X
X
BVOC-GC
Noxy Interc.
E
E
A
X
A
A
A
E
X
A
A
X
X
X
A
E
X
X
E
E
E
E
X
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X
X
NO-RR
NOy
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
NO2+
NO2
NO
Associated
ACTRIS partner
EMEP
REG
GLOB
REG
REG
GLOB
NMHC-GC
HPB
MEL
SSL
ZSF
NGL
SMU
WAL
ZGT
FKL
MHD
IPR
CMN
CBW
AMO
CVO
HRL
UBA
BUL
CH
CH
CZE
FIN
FIN
FRA
FRA
FRA
FRA
FRA
FRA
GER
GER
GER
GER
GER
GER
GER
GER
GRE
IRE
ITA
ITA
NET
UK
UK
UK
GER
GER
GER
GER
GER
USA
NOx EBAS
PUY
GAW
BEO
JFJ
RIG
KOS
PAL
SMR
PEY
TRD
country
BEO Moussala
Jungfraujoch
Rigi-Seebodenalp
Kosetice Observatory
Pallas-Sodankylä
Hyytiälä (SMEAR II)
Peyrusse-Vieille
La Tardière
Revin
Cap Corse
Puy de Dome
SIRTA
Hohenpeissenberg
Melpitz
Schauinsland
Zugspitze Schneef.
Neuglobsow
Schmücke
Waldhof
Zingst
Finokalia
Mace Head
JRC Ispra
Monte Cimone
Cabauw ECN/KNMI
Auchencorth Moss
Cape Verde / York
Harwell
Langen UBA Lab
Jülich WCCNOx/PEGASOS
Garmisch WCC-VOC
MPI Mainz
IUP-Uni Heidelberg
Los Gatos Res.
GAW code
SITE
X
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X
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A
X
E
X
E
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E
E
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X
4
How do stations measure?
Status Stations –
Measurement Techniques and QA/QC
See www.actris.net wp4Documents/StationQuestionnaires
Air Inlet
Sampling
Preconcentration
Instrument
Operation, Maintenance
Data acq. And processing
QA/QC, documentation
Data submission
Sketch of system
Chromatograms
VOC
X
X
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X
X
X
X
X
X
X
NOx
X
X
X
X
X
X
X
5
DQO of ACTRIS and GAW
VOC
What are the recommendations?
How can the stations improve?
Draft Measurement Guidelines
See www.actris.net wp4Documents
NOx
• Rational and objectives
• Data Quality Objectives
• measurement set-up and sampling
• measurement instruments
• calibration
• QA and QC
• data evaluation
• uncertainty
• data submission
6
ACTRIS Round Robin Experiments
Two Legs - ACTRIS 1 /2
NO: synthetic mixture ppm in N2
Actris 1
20%
Actris 2
10%
0%
-10%
HPB
SIRTA
MD-DCE
JFJ
RIG
MEL
FZ-J
PUY-2
PUY
SSL
UBA
HPB
PUY-2
HPB
FKL
FMI
SMR
IPR
CVO
AMO
-20%
CHMI
NO-results RR_2012
+ 3% DQO
- 3% DQO
HPB
NO, relative deviation from NPL reference value
How good are the
calibration standards at the stations?
7
VOC-round robin:
1ppb NMHC in N2
(expand. combined
uncertainty, k=2)
isoprene
8
Deviation < ACTRIS DQO
Deviation < GAW DQO
Dev. < uncertainty, > GAW DQO
Dev. > uncertainty, > GAW DQO
2-methylbutane
n-hexnane
2-methylpentane
n-heptane
n-octane
i-octane
trans-2-butene
cis-2-butene
1,3-butadiene
1-pentene
trans-2-pentene
isoprene
Ethyne
Benzene
Toluene
Ethylbenzene
m,p-xylene
o-xylene
1.3
0.8
0.8
0.3
1.4
1.9
2.0
2.0
1.6
4.3
0.6
0.9
1.5
1.7
0.8
0.9
1.6
-0.1
-1.2
1.4
2.9
-3.9
-2.4
3.9
26
4.4
45.2
6.3
30.1
29.7
2.9
4.8
3.9
1.3
2.2
-3.5
13.1
11.2
-2.8
6.2
9.8
9.4
6.0
4.8
4.0
2.3
4.5
-0.9
0.0
2.3
26
2.0
1.4
0.5
3.8
2.3
2.7
2.9
4.6
2.4
3.7
1.4
0.9
4.2
0.6
0.0
2.3
2.5
4.5
3.7
1.6
4.2
3.0
9.4
20.5
20.8
21.7
26
5.3
5.7
2.0
2.5
0.8
0.4
7.2
6.4
5.5
4.4
1.2
0.1
-0.1
0.6
-0.7
2.0
1.9
3.4
1.7
2.3
3.9
-1.2
8.4
7.9
24
0.1
1.2
1.4
0.8
1.6
-0.6
7.2
4.1
4.9
7.4
4.3
3.1
-0.2
-0.1
0.2
1.3
-1.2
-0.1
0.4
0.4
6.9
5.1
9.1
9.5
9.5
8.1
26
0.1
4.6
5.1
4.4
2.5
3.1
3.4
2.6
2.8
2.7
2.7
-22.7
6.4
2.2
5.0
3.5
3.2
5.1
4.0
2.8
-95.2
4.7
6.1
8.0
10.6
8.4
26
2.4
-1.8
-8.5
-14.9
-1.1
-6.2
-9.4
8
-1.6
-1.2
-51.8
7
-2.8
-4.5
3.6
6.2
3.0
26
3.8
5.2
8.4
10.8
7.6
5
7.2
5.2
7.0
7.2
5.6
26
13.7
13.2
14.9
17.9
13.2
6
0.9
2.5
2.8
7.3
2.5
26
-17.9 -12.0
-4.4
-1.2
-9.3
4.3
-5.5
-6.3
-1.3
4.4
-1.7
-0.3
Propene
Ethene
-2.9
6.4
-0.4
-7.3
18.6
-4.5
-9.3
-4.5
-4.0
2.1
-13.6
-8.5
-2.9
-1.9
-1.9
-1.8
-1.0
-1.1
-3.1
-0.1
70.5
1.6
6.4
8.6
11.3
2.9
1.9
-1.7
-5.6
4.3
4.0
3.0
1.9
2.2
5.2
5.8
5.6
3.2
10.6
16.0
5.8
11.8
5.9
4.8
8.4
4.1
1.4
2.2
2.1
-3.1
-6.9
-4.7
-7.4
-4.4
-2.8
-5.1
-1.3
0.5
0.7
0.5
-0.4
-1.5
-0.1
2.1
-0.4
0.5
1.1
-0.5
1.9
1.3
3.1
1.2
2.2
2.2
3.6
2.0
4.9
0.8
1.0
0.4
1.7
2.9
3.2
2.1
-1.3
-5.8
0.0
66.8
-4.5
3.1
3.8
8.9
11.8
2.7
7
5
-36.6
-121.3 -60.6
N (compounds)
2-methylpropane
1.9
1-butene
n-butane
3.4
-4.1
n-pentane
Propane
YRK
AUC
HAR
RIG
DOU
IPR
JFJ
SIR
PUY
MHD
KOS_A
KOS_B
PAL
SMR
NILU
HPB_A
HPB_B (FID)
HPB_B (MS)
FJZ
ZSF
CMN
N (stations)
Ethane
station/
compounds
VOC-round robin: 1ppb NMHC in N2 (Numbers = % deviations, green < ACTRIS DQO)
-1.5
17.3
13.6
32.1
17.6
-1.9
-13.0
-9.1
-0.6
-21.6 -387
-0.3
1.2
-0.1
-0.3
3.2
0.6
2.2
3.6
-0.8
4.0
1.4
6.2
4.4
-3.5
15.5
2.0
3.7
5.2
8.6
2.9
21
1.3
3.3
2.5
1.9
3.9
5.0
2.0
3.0
-0.8
-1.8
1.1
4.0
0.1
21
50.9
14.6
-7.6
-7.9
3.7
-35.5
2.5
-2.9
11.0
2.7
29.9
9.6
20
16.8 -27.4 21.7
20.1
19.1
17.1
26.4
19.6
17.0
21.8
28.9
0.8
1.4
3.9
0.7
25
-20.0 19.7
20.1
-1.5
3.2
13.7
7.1
5.7
28.6
21
3.6
-145 -90.1 -42.6 -64.3
-13.3
6.1
13.6
9
1.0
13
14
17
16
17
17
16
14
16
14
12
11
12
14
14
14
14
13
13
16
12
18
18
19
16
18
12
12
8
11
12
11
10
9
12
11
10
7
8
8
9
9
8
10
10
11
8
15
11
10
4
7
1
2
4
2
2
2
5
2
3
2
2
3
4
3
5
5
2
2
4
2
1
4
6
7
7
2
1
1
2
2
2
3
2
2
2
1
1
2
1
1
1
1
1
1
1
1
1
1
2
1
2
2
1
2
3
3
4
9
What is the quality
of ambient measurements?
YR K
AUC
HAR
R IG
DOU
IP R
JFJ
S IR
P UY
MHD
KOS _ A
P AL
S MR
NILU
HP B_ A
HP B_ B (MS )
F ZJ
ZS F
C MN
N (s tations )
3
-3
5
-1
5
2
-2
2
2
0
0
2
3
-3
3
39
6
2
4
2
-17
5
10
6
4
6
6
-7
3
32
5
1
5
1
-10
-13
1
0
2
34
8
-7
3
1
-7
4
0
0
-13 -23
-1 74
-1
0
2
2
-3
13
12
-3
12
14
13
1
1
-11 -2
1 -30 37 -39
5
5
0
0
1
-6 -3 -71
-30 -65 1
20 19 30 13 -9 19
-5 -59 6 -17 -415 -177
3
15 13 16 15 15 13
1
4
7
8
9
5
8
1
4
4
3
5
3
1
1
2
2
3
1
1
1
7
2
1
1
2
3
0
9
2
7
4
6
7
4
4
3
1
1
3
2
5
0
1
9
9
2
5
10
17 -12 37
-1 -17
5
1
1
1
17
5
6
15
-23 9
17
28
12
21 24 -23 0 -12
8
14 -24 32 -2 16
-42 0 -18 -6 -23
9 -17 -18 0
-32 2
6
-4
14 32 23
6 -12
-4 23 17
90
-6
24
10
-29
-24
10
1
14
9
-1
3
-50
-2
23
43
-33
-6
-29
4
-1 10
-8 -6
3
-12 -15
-42
-3
-85 -26 -75
15 12 11
2
9
10
2
1
1
1
2
1
6
3
9
57
4
11
10
-1
0
-4
0
5
4
1
3
11
5
4
1
1
21
-37
38
4
-412
6 -16
-10 34
12 10
3
5
4
7
1
2
4
4
1
2
1
34
6
16
2
1
1
8
-1 13
-27 -34 -121
40 54 -61
-48 -970 34
12 13 12
3
5
3
6
4
3
2
3
5
1
1
1
23
-23
27
-7 -12
-25 -26
7
2
-20 -34
-200 -5
20 16
6
12
9
3
4
4
11
6
4
1
2
1
1
33
6
8
-7
9
18
-259
10
0
21
14 12
3
13
6
1
3
-14
3
1
1
1
o-xylene
m,p-xylene
E thylbenz ene
T oluene
B enz ene
P ropyne *
E thyne
Is oprene *
2-methyl-2-butene
cis -pentene *
trans -2-pentene *
1-pentene *
1,3-butadiene *
cis -2-butene *
trans -2-butene *
2-methylpropene
1-butene
P ropene
E thene
C yclohexane
2,2,4-trimethylpentane
n-octane *
3
26
-6
1
4
10
0
n-heptane
2 -10 -4
1 -44 -38
-1 -138 -82
18
-57
7
0 -200
33
-2
-1
-1
-3
1
2,3-dimethylbutane *
-40 -37
0 -54
10 27
-1 15
6 -23 -1 -37 56
-2 -3 -40 -54
-14 1
-5
-22
1
1
4
2,2-dimethylbutane
3-methylpentane
2-methylpentane
n-hexnane
2-methylbutane
n-pentane
2-methylpropane
n-butane
P ropane
E thane
s tation/compounds
VOC whole air intercomparison during round
robin experiment
-7 -20 -53 -49 -29
-8 -1 -27
0
8
6
14 20
3
-7
7 -18 -1 -5
0
4
11
0
4
8
3 -14
-4 12
8
-6
-12 -5 10 24 -6
-53
9
-8
4
15
2
5
4
7
-31
3
-12
2
10
-9
-3
-2
-3
0
-4
-2
9
0
16
6
9
1
-3 -1 -2
3
-6
3
2
-2
7
11 11 31
-11 -38 -13 -16
-4
5
17 11
16 15 15 16
5
7
5
10
5
2
2
2
3
2
5
2
3
4
3
2
10
Et
h
Et ane
Pr h en
o e
2- Pr pan
m op e
et e
hy n
e
n- lpr
o
Ac but p
e an
t-2 ty le e
-b ne
1- ute
c - bu ne
2 te
2- -bu ne
m te
et n
h e
n
1, -p y lb
3- en u
bu ta t
t-2 tad n e
-p ie
n
1- ent e
2- pe en
m nt e
-p en
e
n- nta e
he ne
is x an
n- opr e
he en
p e
2, be tan
2, nz e
4- e
tm ne
n- -pe
oc n
ta t
et
hy to ne
lb l ue
en n
e
o- zen
p x e
1, ,m y len
3, -x e
1, 5 -t yl e
2, m ne
1, 4 -tm-be
2, - n z
3 b
al -tm en
ph -b z
a- en
p z
m inen
yr e
c
3- en
p ca e
Deviations from Reference values for one station (orange: VOC in N2, green: VOC in air)
FID-C-Response as diagnostic tool (blue: lab-standard, red: ACTRIS VOC in N2)
1.8
Lab-Stand
Auch1+2
C- Resp_VOC- N2
Dev- VOC- N2
Dev- VOC- air
1
0.2
11
•14 NO/NO2 instruments sampling from a common manifold at
Hohenpeissenberg, Nov, 12.-16., 2012
• 10x CLD with PLC/BLC or Mo converters, 1x LIF, 1x DOAS, 1x
CAPS, 1x CRD
• initial calibration at the beginning of SBS via manifold
• zero gas, synthetic mixtures, ambient air, and spiked ambient air
12
Time-series ambient
14
NO2 HPB
NO2 FZJ
NO2 IPR
12
NO2 CVO
NO2 CHMI
NO2 PUY
10
NO2 MD-DCE
NO2 Sirta
NO2 FMI
NO2 [ppb]
8
NO2 CYI
NO2 DOAS
NO2 LIF
NO2 LGR (corr)
6
NO2 CAPS
4
2
0
13. Nov. 12
14. Nov. 12
15. Nov. 12
16. Nov. 12
-2
13
Feed-Back-Plots
14
Performance of patricipating instruments in air: <20% of data outside DQO,
>50% of data outside DQO
HPB
# NO measurements
% NO not in DQO
# NO2 measurements
% NO2 not in DQO
2689
5%
2697
17%
FZJ
IPR
2907
8%
2510
64%
2882
17%
2882
88%
CVO
2953
16%
2976
58%
CHMI
2963
34%
2967
96%
PUY
2787
96%
2787
36%
MD-DCE
2825
55%
2819
14%
Sirta
2928
46%
2946
57%
FMI
CYI
2854
19%
2859
100%
1450
53%
1499
52%
DOAS
2727
14%
DOAScorr.
2727
7%
LIF
2185
58%
LIF-corr.
2185
16%
LGR
2246
92%
CAPS
2826
10%
Table 6.5: Performance of the participating instruments in ambient air measurements with respect to
DQO by means of the total number of NO (NO2) measurements and the percentage of data
falling outside the DQO range (see figures in Annex 3) are given; green: less than 20% and
orange: more than 50% of data worse than DQO
15
Improve quality,
disseminate knowledge,
Increase data availability
expand network
• round robin VOC + monoterpenes + side-by-side NOx
– stations got feed-back and questions - waiting for station answers
• learn about superior techniques, problematic techniques – input for
Measurement Guidelines and QA, distribute in community, improve
• upcoming OVOC intercomparison with GC-MS/FID and PTR-MS instruments at
Hohenpeissenberg in October
• papers on RR and comparisons-results
• next version Draft Measurement Guidelines – ACTRIS + GAW community –
Cross-link with IAGOS, PEGASOS, iLeaps, AQUILA - finalize in GAW Reports
• station audits
• EBAS data reporting feed-back (data evaluations)
Acknowledgement
The research leading to these results has received funding from the European Union Seventh Framework Programme
(FP7/2007-2013) under grant agreement n° 262254.
16