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Meteorologisches Observatorium Hohenpeißenberg. VOC MEASUREMENTS AT HOHENPEISSENBERG AS PART OF THE GAW PROGRAM. Christian Plass-Dülmer and Harald Berresheim Meteorologisches Observatorium Hohenpeißenberg, DWD, Germany. VOC Monitoring - Objectives. GAW expert meeting Report 111, 1995

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Meteorologisches Observatorium Hohenpeißenberg

VOC MEASUREMENTS AT HOHENPEISSENBERG AS PART OF THE GAW PROGRAM

Christian Plass-Dülmer and Harald Berresheim

Meteorologisches Observatorium Hohenpeißenberg, DWD, Germany


VOC Monitoring - Objectives

  • GAW

  • expert meeting Report 111, 1995

  • Global distribution, seasonality and trends

  • understanding the biogeochemical cycling (sources, sinks, chemistry)

  • impact on ozone, photooxidants, oxidising capacity, aerosol, climate, health

  • WMO (1995): WMO-BMBF Workshop on VOC - Establishment of a „World Calibration/Instrument Intercomparison Facility for VOC“ to Serve the WMO Global Atmosphere Watch (GAW) Programme, WMO Report, 111.

  • EMEP

  • Strategic Plan 2004

  • European distribution and trends

  • Compliance monitoring (compliance with protocols)

  • understand physical and chemical processes

  • Support for EMEP model

  • EMEP (2003): The EMEP Monitoring Strategy 2004-2009 - Background document with justification and specification of the EMEP monitoring programme 2004-2009, eds. Kjetil Torseth and Oystein Hov, EMEP, CCC-Report 9/2003.


GAW-Program VOC:

MOHp

  • Stage 1: C2-C9 hydrocarbons HC

  • Stage 2: C10-C14 HC (biogenic)

  • Stage 3: oxygenated VOC (OVOC)

  • GC-FID

  • GC-MS/FID

  • GC-PDHID/FID

Measurements at1:00 and 13:00 CETca. 80 VOC

Detection limits: 1 ppt ... 10 ppt

Accuracy: C2-C9 HC 5-25%, Terpenes 20-40%

QA and QC Procedures

VOC Intercomparisons: NOMHICE, AMOHA, and GAW




Biogenic VOC at Hohenpeißenberg

monthly means of noon-time concentrations (preliminary data)


Annual cycles of noon- and midnight monthly mean concentrations

Summer ratio day/night: Dt [OH] = 1-4 1010 s molec/cm³

c(day) = c(night) exp(-k[OH]Dt)


Turn over-rates due to reactions with OH radicals concentrations

Jun-Aug Dec-Feb,

10 106 molecules/(cm³s) 3.5 106 molecules/(cm³s)

(2004 data at noon time and measured OH)


Research Topics at Hohenpeißenberg with respect to VOC concentrations

  • trends and distribution HC, OVOC‘s

  • oxidizing capacity VOC turn-over, radical precursors

  • aerosol formation and growth semi-volatile prod.

  • oxidant formation VOCturn-over

  • source attribution tracer, signature

Isoprene, monoterpenes, light alkenes, formaldehyde

semi-volatile products of monoterpenes and aromatics

various C2-C10 hydrocarbons, OVOC‘s and halogenated VOC


Future Requirements concentrations(presented at GAW workshop Tutzing 2004)

  • Stations: report VOC+errors to WDCGG/EMEP

  • SAG: establish DQO‘s, QA/QC procedures, Pilot stations, SOP‘s, error assessment

  • WCC: continue audits+intercomp., provide standards, SOP‘s, error assessment, data evaluation

  • QA/SAC: support SAG, WCC, and stations; motivate and coordinate

  • scientific user: analyse spatial distributions and temporal evolution, sources and sinks

  • all: workshops/conferences to communicate



GC-2 concentrations

Varian 3400CX MS/FID

C5-C14 Hydrocarbons

Halocarbons

Oxygenated VOC


GC-1 concentrations

Varian 3600CX, FID

C2-C8 Hydrocarbons


Glass-Sampling Line concentrations


VOC patterns of boundary-layer and free troposphere air concentrations

Ethan

Propan

i-Butan

n-Butan

i-Pentan

n-Pentan

2-M-Pentan

n-Hexan

n-Heptan

Ethen

Propen

1,3-Butadien

Isopren

Acetylen

Propin

Benzol

Toluol

Ethylbenzol

Boundary-layer

p,m-Xylol

Free troposphere

o-Xylol

1

10

100

1000

Mixing ratios, pptv

Photochemical age:

about 8 days


X concentrations

10

Ratios Winter/Summer

Measurement

Lifetime

1

Ethan

Toluol

Benzol

Propan

i-Butan

Propen

Ethen

Propin

n-Butan

i-Pentan

Acetylen

n-Pentan

1-Buten

p,m-Xylol

t-2-Buten

1,3-Butadien

Annual Cycle: Winter-Summer Ratios of selected VOC

Box:

Atmosphere

OH O3

T=1/(K[OH]+k[O3])

VOC-emissions = const.

T-Winter MR-Winter

OH O3

Nov-Feb 0.2E6 cm-³ 32 ppb

Jun-Aug 1.7E6 cm-³ 51 ppb

Despite of chemical impacts, sources and meteorology are important

=

T-Summer MR-Summer


10000 concentrations

X

1000

100

mean mixing ratio 1998, pptv

Alkanes

Alkenes

10

Alkynes

Aromatics

1

1E-13

1E-12

1E-11

1E-10

k(OH), cm³/(s molecule)

Mixing Ratios 1998vs. reactivity with OH


Biogenic Emissions - mixing ratios versus temperature concentrations

1000

Sum of Terpenes

Isoprene

800

---> Emission driven by temperature (meteorology)

---> Ozone-smog

600

---> Particle-formation

---> climate !

Mixing Ratio, pptv

400

200

0

-10

-5

0

5

10

15

20

25

30

Temperature, °C


5% concentrations

x

0%

linear Trend, %/year

Alkanes

-5%

Alkenes

Alkynes

Aromatics

-10%

1E-13

1E-12

1E-11

1E-10

k(OH), cm³/(s molecule)

Do we see changes in the composition of anthropogenic VOC?

Trends are still uncertain due to the short observation periode!


C2-C7 n-alkanes concentrations

C4-C7 i-alkanes

C2-C6 alkenes

C7-C8 aromatics


VOC Monitoring Program concentrations

NMHC Measurements by GC/FID - canister / on-line

  • GAW

  • stage 1: C2-C9 hydrocarbons

  • stage 2: C10-C14 hydrocarbons

  • stage 3: oxygenated VOC

  • establish 3 pilot stations

  • EMEP

  • level 2: C2-C7 hydrocarbons

  • level 2: C1-C6 carbonyls

  • level 3: C6-C12 hydrocarbons

  • level 2 = approx 15 sites

  • level 3 = research stations

GAW/EMEP: 30 target compounds C2-C9


VOC QA / QC concentrations

  • GAW

  • Report 111, ...

  • Intercomp.+audits by WCC

  • training (GAWTEC)

  • EMEP

  • Manual (EMEP/CCC-1/95)

  • intercomp.+audits by NILU

  • data screening by NILU and local laboratories

VOC Data Quality Objectives

accuracy NMHC: 10 - 20 %

accuracy NMHC 15-25%

no calibration gas standards

no QA / QC protocolSOP‘s ?


Yearly „Trend“ of anthropogenic VOC: Measurements and Estimates

DWD

estimated

estimated

Hohenpeißen-

UBA/EMEP

emissions

emissions

berg

Waldhof

(UBA )

(UBA )

1998-2003

1992-2002

1990-2001

2000-2001

Measurements

-4%

-5%

Transport Emissions

-12%

0%

total (without solvents)

-10%

0%

(National Emission-Inventory Germany - 2002, UBA, 31/07/03)



Annual winter (Nov-Feb) median concentrations of hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab.

Reference:

VOC Measurements 2002

Sverre Solberg, NILU, Kjeller, Norway

EMEP / CCC-Report 8/2004

Reference O-92016


Mixing ratios 1998 versus reactivity towards OH hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab.


QC - Recent International Intercomparison Experiments hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab.

NOMHICE: analytical preformance of participating labs

AMOHA: analytical preformance + canisters + sampling procedure

GAW-WCC: analytical preformance + on-line / canister

NOMHICE - NonMethane Hydrocarbon InterComparison ExperimentTasks 1 - 5 (Apel et al., JGR, 1994, 1999, 2003)

AMOHA - Accurate Measurements of Hydrocarbons in the AtmosphereTasks 1 - 3 (Slemr et al., 2002)Task 4 (Plass-Dülmer et al., in preparation)

First GAW - WCC - VOC - Intercomparison 2003

B. Rappenglück et al.


First GAW - VOC Intercomparison 2003 hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab.

Task-1: Synthetic Mixture (73 components, 0.2-10 ppb)

Task-2: ambient air - parallel sampling participant / WCC

  • Task-1

  • 62 % within Data Quality Objectives (30 Target Compounds)

See poster by Rappenglück et al.


VOC Monitoring in Europe hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab. - EMEP network (since 1992)

GAW Global Stations

Zeppelin

Pallas, since 1992

Birkenes

Hohenpeissenberg, since 1998

Mace Head,

since 2001 ?

Izana, no VOC


VOC Distribution (median) in Winter-Months 2002 hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab.

(EMEP VOC Report, 2004)

Lifetime: ca. 60 days


EMEP Trend Results hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab.

no clear trends in Northern Europe (Finnish sites)

decreasing concentrations in Central Europe(20-50% / 1992-2000)

and a levelling off after 2000

Caution: Trends are uncertain


Summary hydrocarbons at Waldhof (DE), Kosetice (CZ) and Donon (FR), red letters are results by NILU analysis, blue by national lab.

  • GAW and EMEP: similar objectives, VOC compounds, and QA /QC

  • VOC intercomparisons: - Data Quality Objectives are met by 2/3 of results - data quality varies substantially from lab to lab - problem: error assessment (DQO)

  • European VOC monitoring is mainly provided by EMEP

  • Results of European monitoring: - higher concentrations in Central and Eastern Europe - trends of anthr. VOC in Central Europe by 0-10% / year


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