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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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slide1
Meteorologisches Observatorium Hohenpeißenberg

VOC MEASUREMENTS AT HOHENPEISSENBERG AS PART OF THE GAW PROGRAM

Christian Plass-Dülmer and Harald Berresheim

Meteorologisches Observatorium Hohenpeißenberg, DWD, Germany

slide2
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.
slide3
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

slide7
Biogenic VOC at Hohenpeißenberg

monthly means of noon-time concentrations (preliminary data)

slide8
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)

slide9
Turn over-rates due to reactions with OH radicals

Jun-Aug Dec-Feb,

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

(2004 data at noon time and measured OH)

slide10
Research Topics at Hohenpeißenberg with respect to VOC
  • 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

slide11
Future Requirements (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
slide13
GC-2

Varian 3400CX MS/FID

C5-C14 Hydrocarbons

Halocarbons

Oxygenated VOC

slide14
GC-1

Varian 3600CX, FID

C2-C8 Hydrocarbons

slide17
VOC patterns of boundary-layer and free troposphere air

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

slide18
X

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

slide20
10000

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

slide21
Biogenic Emissions - mixing ratios versus temperature

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

slide22
5%

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!

slide23
C2-C7 n-alkanes

C4-C7 i-alkanes

C2-C6 alkenes

C7-C8 aromatics

slide24
VOC Monitoring Program

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

slide25
VOC QA / QC
  • 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 ?

slide26
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)

slide28
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

slide30
QC - Recent International Intercomparison Experiments

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.

slide31
First GAW - VOC Intercomparison 2003

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.

slide32
VOC Monitoring in Europe - EMEP network (since 1992)

GAW Global Stations

Zeppelin

Pallas, since 1992

Birkenes

Hohenpeissenberg, since 1998

Mace Head,

since 2001 ?

Izana, no VOC

slide33
VOC Distribution (median) in Winter-Months 2002

(EMEP VOC Report, 2004)

Lifetime: ca. 60 days

slide34
EMEP Trend Results

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

slide35
Summary
  • 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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