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 geographical coverage (at WDCGG)

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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

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1.00

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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%

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1995 2000 2005 2010

rel. SO

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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

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Jan Feb Mrz Apr Mai Jun Jul Aug Sep Okt Nov Dez

SO2 [ppb

]

1 ppb ≈ 3 µg/m³

HPB

ZSF

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Examples for use of SO 2 data (II)

SAG RG Meeting Malta, 29th­30th March 2011

SO 2 & particle > 3 nm at SFH & HPB

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time of day

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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

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O3 [ppb

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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.