1
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
2
WP4: Trace gases networking: Volatile organic carbon and nitrogen oxides
WMO/GAW
WCC / QA-SAC
CCL
EMEP
Data Quality Objective
Meas. Guidelines
Qualtity Assurance
Data Reporting
Integration/HarmonizationFunding
ACTRIS-VOC/NOx ActivitiesAMOHAFP5 project
3
ACTRIS NA4 CommunityWork shop Ispra, Oct 2011, Work shop Hohenpeißenberg, June 2012Several bi-lateral meetings
Reactive GasesDevelopment of concepts, drafts, dissemination, revisions in
ACTRIS-GAW CommunityGAW VOC Expert Group, York, Sep 2012WMO/GAW Meeting, Geneva, Feb 2013
ACTRIS-EMEP CommunityEBAS Data workshop, Oslo, May 2012EMEP TFMM , May 2011, May 2013
ACTRIS-AQUILA CommunityCooperation in method development,Participate in RR and intercomparisons
4
SITE
GA
W c
ode
coun
try
GA
W
EM
EP
AC
TR
IS p
artn
er
Ass
ocia
ted
NO
NO
2
NO
2+
NO
y
NO
-RR
Nox
y In
terc
.
NO
x E
BA
S
NM
HC
-GC
OV
OC
BV
OC
-GC
PT
RM
S
NM
HC
-RR
BV
OC
-RR
VO
C E
BA
S
BEO Moussala BEO BUL REG X X X XJungfraujoch JFJ CH GLOB X X X X X E X X ARigi-Seebodenalp RIG CH REG X X X X E X X AKosetice Observatory KOS CZE REG X X X X X X A X X X APallas-Sodankylä PAL FIN GLOB X X X X X X X X EHyytiälä (SMEAR II) SMR FIN X X X X X X X XPeyrusse-Vieille PEY FRA X X X X X X X A X X X ALa Tardière TRD FRA X X X X X A X X X ARevin FRA X X X X A XCap Corse FRA X X X XPuy de Dome PUY FRA REG X X X X X X A X X X XSIRTA FRA X X X X X X X X XHohenpeissenberg HPB GER GLOB X X X X X X X A X X X X X AMelpitz MEL GER X X X X X ASchauinsland SSL GER REG X X X X X X X EZugspitze Schneef. ZSF GER GLOB X X X X X XNeuglobsow NGL GER CONTR X X X ESchmücke SMU GER CONTR X X X X EWaldhof WAL GER CONTR X X X EZingst ZGT GER CONTR X X X EFinokalia FKL GRE CONTR X X X X XMace Head MHD IRE GLOB X X X XJRC Ispra IPR ITA REG X X X X X X XMonte Cimone CMN ITA GLOB X X X X X ACabauw ECN/KNMI CBW NET X X X X XAuchencorth Moss AMO UK X X X X E X X ECape Verde / York CVO UK GLOB X X X X X X X X XHarwell HRL UK CONTR X E X X ELangen UBA Lab UBA GER X X X XJülich WCCNOx/PEGASOS GER WCC X X X X X X XGarmisch WCC-VOC GER WCC XMPI Mainz MPI GER XIUP-Uni Heidelberg UHEI GER XLos Gatos Res. LGR USA X
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How do stations measure?
Status Stations – Measurement Techniques and QA/QC
See www.actris.net wp4Documents/StationQuestionnaires
VOC NOxAir Inlet X XSampling XPreconcentration XInstrument X XOperation, Maintenance X XData acq. And processing X XQA/QC, documentation X XData submission X XSketch of system X XChromatograms X
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Draft Measurement Guidelines
See www.actris.net wp4Documents
• Rational and objectives• Data Quality Objectives• measurement set-up and sampling• measurement instruments• calibration• QA and QC• data evaluation• uncertainty • data submission
DQO of ACTRIS and GAW
What are the recommendations?How can the stations improve?
VOC
NOx
7
ACTRIS Round Robin ExperimentsTwo Legs - ACTRIS 1 /2
NO: synthetic mixture ppm in N2
How good are the calibration standards at the stations?
-20%
-10%
0%
10%
20%
HP
B
CH
MI
AM
O
CV
O
IPR
SM
R
FM
I
FK
L
HP
B
PU
Y-2
HP
B
UB
A
SS
L
PU
Y
PU
Y-2
FZ
-J
ME
L
RIG
JFJ
MD
-DC
E
SIR
TA
HP
B
NO-results RR_2012+ 3% DQO- 3% DQO
Actris 1 Actris 2
NO
, rel
ative
dev
iatio
n fr
om N
PL re
fere
nce
valu
e
8
VOC-round robin: 1ppb NMHC in N2 (expand. combined uncertainty, k=2)
isoprene
9
stati
on/
com
poun
ds
Etha
ne
Prop
ane
n-bu
tane
2-m
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2-m
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2-m
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tane
n-he
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n-oc
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i-oct
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Ethe
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Prop
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1-bu
tene
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Benz
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N (c
ompo
unds
)
YRK 3.4 1.9 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
AUC -4.1 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
HAR 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
RIG 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
DOU 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
IPR 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
JFJ 2.4 -1.8 -17.9 -12.0 -8.5 -14.9 -2.9 7
SIR 6.4 -0.4 -7.3 18.6 2.1 -1.1 -6.2 -9.4 8
PUY -4.5 -9.3 -4.5 -4.0 -1.6 -1.2 -51.8 7
MHD -4.4 -1.2 -9.3 -13.6 -8.5 5
KOS_A 4.3 -5.5 -6.3 -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 -2.8 -4.5 3.6 6.2 3.0 26
KOS_B 3.8 5.2 8.4 10.8 7.6 5
PAL -1.3 4.4 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 7.2 5.2 7.0 7.2 5.6 26
SMR -36.6 13.7 13.2 14.9 17.9 13.2 6
NILU -1.7 -3.1 -6.9 -4.7 -7.4 -4.4 -2.8 -5.1 -0.3 9
HPB_A -0.3 -1.3 0.5 0.7 0.5 -0.4 -1.5 -0.1 2.1 -0.4 0.5 1.1 -0.5 1.0 1.2 -0.1 -0.3 3.2 0.6 2.2 13.6 0.9 2.5 2.8 7.3 2.5 26
HPB_B (FID) 1.9 1.3 3.1 1.2 2.2 2.2 3.6 2.0 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
HPB_B (MS) 4.9 0.8 1.0 0.4 1.7 2.9 3.2 2.1 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
FJZ -121.3 -60.6 -1.3 -5.8 0.0 66.8 -4.5 3.1 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
ZSF 3.8 -1.5 17.3 13.6 32.1 17.6 8.9 11.8 2.7 3.6 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
CMN -1.9 -13.0 -9.1 -0.6 -21.6 -387 -145 -90.1 -42.6 -64.3 -13.3 6.1 -20.0 19.7 20.1 -1.5 3.2 13.7 7.1 5.7 28.6 21
N (stations) 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 1 1 1 2 2 1 1 2 2
3 2 2 2 1 2 1 1 1 1 1 1 1 2 2 1 3 3 4
Deviation < ACTRIS DQO
Deviation < GAW DQO
Dev. < uncertainty, > GAW DQO
Dev. > uncertainty, > GAW DQO
VOC-round robin: 1ppb NMHC in N2 (Numbers = % deviations, green < ACTRIS DQO)
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What is the quality of ambient measurements?
VOC whole air intercomparison during round robin experiment
stati
on/c
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YRK 3 2 3 5 3 2 0 -54 -40 -37 2 -10 -4 1 10 5 2 17 8 21 24 -23 0 -12 90 24 1 -2 -7 -20 -53 -49 -29AUC -3 2 39 10 32 34 10 27 1 -44 -38 17 -12 37 14 -24 32 -2 16 10 14 8 0 -8 -1 -27HAR 5 0 6 6 5 8 -1 15 -1 -138 -82 5 -1 -17 -42 0 -18 -6 -23 -29 9 -7 3 14 20 6RIG -1 0 2 4 1 -7 6 -23 -1 -37 56 18 9 1 1 1 28 -32 2 9 -17 -18 0 -6 -24 -1 0 7 -18 -1 -5DOU 5 2 4 6 5 3 -2 -3 -40 -54 7 -57 9 6 5 17 12 14 32 23 -4 6 10 3 23 8 4 0 11 4IPR 2 3 2 6 1 1 -14 1 33 0 -200 -23 9 15 -4 23 17 6 -12 -50 8 -4 12 3 -14J FJ -2 -3 -17 -7 -10 -7 -6SIR 3 -13 -23 43 -12 -5 10 24 -6PUY 26 -1 74 -33 -8 9 -53MHD -5 -2 -6 -13 4KOS_A -22 -1 1 1 1 0 0 4 2 5 -6 57 11 38 21 34 16 -7 -12 23 33 2 -3 4 5 -31PAL 1 -1 4 4 0 0 9 6 7 0 -29 4 10 -37 6 -25 -26 -23 6 10 -2 15 4 3SMR 27 -9 -3 2 7 -12NILU -1 2 -3 10 -11 -2 -1 -4 8HPB_A 0 2 1 0 5 1 -30 37 -39 7 4 -1 10 4 9 0 0 4 4 1 1 2 2 7 6 9 -7 -14 0 3 -3 -1 -2HPB_B (MS) 1 0 0 5 3 -8 -6 -1 13 8 -20 -34 18 -4 -2 2 3 -6FZJ -30 -65 1 -6 -3 -71 -12 -15 -412 -27 -34 -121 -200 -5 -259 -2 11 11 31 7ZSF -3 -3 20 19 30 13 -9 19 -3 -42 5 6 -16 40 54 -61 20 16 0 10 9 -11 -38 -13 -16CMN 12 -5 -59 6 -17 -415 -177 -85 -26 -75 -10 34 -48 -970 34 21 0 17 11 5 -4N (s tations ) 13 14 15 13 16 15 15 13 3 4 3 15 12 11 4 11 12 10 4 12 13 12 11 12 4 2 14 12 3 16 16 15 15 16
12 13 8 5 9 8 7 4 1 1 10 9 2 1 5 5 3 1 3 5 3 6 9 4 13 3 1 6 10 5 7 53 5 3 4 4 1 1 1 1 2 3 4 7 4 2 3 4 6 4 3 1 6 1 9 2 2 2 5
1 1 1 1 3 2 2 1 1 1 2 1 1 1 1 5 3 2 1 1 1 2 5 2 33 2 1 1 2 7 1 3 2 3 6 1 2 1 1 1 1 1 3 2 3 4 3
11
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)
0.2
1
1.8
Ethan
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Propa
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Acety
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2,2,
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-xyle
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1,3,
5-tm-b
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1,2,
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1,2,
3-tm-b
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alph
a-pin
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myr
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Auch1+2 C-Resp_VOC-N2 Dev-VOC-N2 Dev-VOC-airLab-Stand
12
•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
13
-2
0
2
4
6
8
10
12
14
13. Nov. 12 14. Nov. 12 15. Nov. 12 16. Nov. 12
NO
2 [p
pb
]
NO2 HPB
NO2 FZJ
NO2 IPR
NO2 CVO
NO2 CHMI
NO2 PUY
NO2 MD-DCE
NO2 Sirta
NO2 FMI
NO2 CYI
NO2 DOAS
NO2 LIF
NO2 LGR (corr)
NO2 CAPS
Time-series ambient
14
Feed-Back-Plots
15
HPB FZJ IPR CVO CHMI PUY MD-DCE Sirta FMI CYI DOASDOAS-corr.
LIF LIF-corr. LGR CAPS
# NO measurements 2689 2907 2882 2953 2963 2787 2825 2928 2854 1450% NO not in DQO 5% 8% 17% 16% 34% 96% 55% 46% 19% 53%# NO2 measurements 2697 2510 2882 2976 2967 2787 2819 2946 2859 1499 2727 2727 2185 2185 2246 2826% NO2 not in DQO 17% 64% 88% 58% 96% 36% 14% 57% 100% 52% 14% 7% 58% 16% 92% 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
Performance of patricipating instruments in air: <20% of data outside DQO, >50% of data outside DQO
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• 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)
AcknowledgementThe research leading to these results has received funding from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement n° 262254.
Improve quality, disseminate knowledge,Increase data availability
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