SAG RG Meeting Malta, 29th30th March 2011
Measurements sulphur dioxide in GAW status and further needs Stefan Gilge, Christian PlassDuelmer
German Meteorological Service Hohenpeissenberg Meteorological Observatory
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SAG RG Meeting Malta, 29th30th March 2011
German Meteorological Service Hohenpeissenberg Meteorological Observatory
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SO 2 : sources and sinks § sources: anthropogenic and natural in proportion 2:1 (global)
anthrop.: large combustion plants (power plants), industry & commerce, domestic home, (shipping) traffic, diffuse sources
natural: H 2 S, DMS emission from sea, forest fires, vulcanos
§ sinks: oxidation in gas phase (OH, O 3 ) liquid phase (H 2 O 2 , O 3 and other oxidants) heterogeneous phase (incl. catalytic reactions)
fractions of SO 2 oxidation strongly depends on numerous parameters like meteorological conditions, pH, additional trace substances …
§ life time: about 28 days
SAG RG Meeting Malta, 29th30th March 2011
German Meteorological Service Hohenpeissenberg Meteorological Observatory
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motivation for measurement of SO 2 : § toxic at higher concentration (Maximum Permissible Concentration: 1.3 mg/m³)
London Smog (5.12.1952): 3,8 mg/m³ SO 2 (a.o.) ; 400012000 victims
mean concentration in Western Europe today about 34 orders of magnitude below „London Smog“
§ trend of emission reduction
§ precursor of sulphuric acid (acid rain)
§ precursor of sulfate aerosol (“anti greenhouse effect”)
§ tracer for better evaluation of air mass origin (e.g. volcanic eruptions)
§ …
SAG RG Meeting Malta, 29th30th March 2011
German Meteorological Service Hohenpeissenberg Meteorological Observatory
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measurement techniques: § EMEP: alkaline impregnated filter (pack) and ion chromatography
§ EMEP: coated annular denuder & ion chromatography
§ chemiluminescence: HSO 3 + Ce 4+ → HSO 3 * + Ce 3+
2 HSO 3 * → S 2 O 6 2 + 2 H +
S 2 O 6 2 → SO 2 * + SO 4 2
SO 2 * → SO 2
§ COSO2: electrochemical, SO 2 + J 2 + 2 H 2 0 → SO 4 2 + 2 J
§ TCM: photometry after reaction of SO 2 with tetrachloromercurate
§ UV fluorescence (absorption: 190230 nm, emission: 220400 nm), possible to enhance sensitivity by means of 2 nd channel (SO 2 removed)
§ DOAS
§ satellite applications
§ …
SAG RG Meeting Malta, 29th30th March 2011 5
1978 1983 1988 1993 1998 2003 2008
• 49 sites , most started at the beginning of the nineties
SO 2 temporal coverage (at WDCGG)
SAG RG Meeting Malta, 29th30th March 2011
SO 2 time series and trends (I)
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SO 2 time series (12 month running mean) at selected GAW sites
0.01
0.10
1.00
10.00
100.00
1985 1990 1995 2000 2005 2010
SO2 [ppb
]
Kosetice
Leba
Zoseni
HPB
ZSF Zeppelinfjellet
JFJ
Jakarta
BKT
SAG RG Meeting Malta, 29th30th March 2011 8
SO 2 relative time series (deviation of 12 month r.m. from mean (1995end)) at selected GAW sites
0%
50%
100%
150%
200%
250%
300%
350%
1995 2000 2005 2010
rel. SO
2
Kosetice
Leba
Zoseni
HPB
ZSF
Zeppelinfjellet
JFJ
Jakarta
BKT
SO 2 time series and trends (II)
SAG RG Meeting Malta, 29th30th March 2011
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Jan Feb Mrz Apr Mai Jun Jul Aug Sep Okt Nov Dez
SO2 [ppb
]
1 ppb ≈ 3 µg/m³
HPB
ZSF
9
Examples for use of SO 2 data (II)
SAG RG Meeting Malta, 29th30th March 2011
SO 2 & particle > 3 nm at SFH & HPB
0
1
2
3
4
5
6
7
00 02 04 06 08 10 12 14 16 18 20 22 00 02 04 06 08 10 12 14 16 18 20 22 00 02 04 06
time of day
SO2 [ppb
]
0
20000
40000
60000
80000
100000
120000
140000
particle > 3nm
[nu
mber
/cm³]
SO2 SFH SO2 HPB particle SFH particle HPB
May, 19 th May, 18 th May, 20 th
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Examples for use of SO 2 data (I)
SAG RG Meeting Malta, 29th30th March 2011 11
SO2 & O3 at Schneefernerhaus, Dec., 12th 2009
0.0
0.5
1.0
1.5
2.0
2.5
3.0
00 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23
SO2 [ppb
]
0
5
10
15
20
25
30
O3 [ppb
]
SO2 SFH [ppb] O3 SFH [ppb]
Examples for use of SO 2 data (III)
SAG RG Meeting Malta, 29th30th March 2011
German Meteorological Service Hohenpeissenberg Meteorological Observatory
Current Situation: • responsibility: SAG for Reactive Gases • WDCGG • some data from only European sites and Indonesia with different _measuring methods and perhaps questionable data quality • growing emissions in Asia • strong scientific interest in reliable SO 2 data
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But • no QA / SAC • no DQO : no precision and accuracy or data completeness goals • no SOPs • no CCL / no primary standard • no WCC
SAG RG Meeting Malta, 29th30th March 2011
German Meteorological Service Hohenpeissenberg Meteorological Observatory
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Future needs: • Setup of DQO‘s and SOP‘s for suphur dioxide
• Implementation of SO 2 measurements at more GAW sites, especially in Asia and North America
• Intercomparison experiments to ensure comparability of different measurement methods (EMEP Filter Pack vs. UVAbsorption, …)
• Implementation of CCL and WCC
• Implementation of new instruments to get a link between ground based measurements and satellite applications
Details should be discussed at an upcoming workshop on SO 2 in 2012
In the face of growing SO 2 emissions in Asia and in the light that most central GAW facilities are in Europe/America, a WCC/CCL in Asia is
suggested.