A EUROPEAN AEROSOL PHENOMENOLOGY: TOTAL CARBON, ELEMENTAL CARBON

AND ABSORPTION COEFFICIENT

Fabrizia CavalliEuropean Commission – DG Joint Research Centre

M. ZanattaLaboratory of Glaciology and Geophysics of Environment, St Martin d'Hères Cedex

Paul Scherrer Institute, Laboratory of Atmospheric Chemistry, Villigen

The ACTRIS COMMUNITY

▪ TOTAL CARBON, ELEMENTAL CARBON, PM MASS, ABSORPTION COEFFICIENT AND THEIR RATIOS, in PM2.5 and in PM10

▪ 10 EUROPEAN REGIONAL BACKGROUND SUPER-SITES

▪ 4 YEARS of data: 2008 – 2011 (different data coverage across the network)

FINOKALIA

BIRKENES

VAVIHILL

ASPVRETEN

HARWELL MELPITZKOSETICE

PUY de DÔMEISPRA

MONTSENY

NORDIC

CONTINENTAL

HIGH ALTITUDE

MEDITERRANEAN

CONTENT of the STUDY:

COMMON STANDARDISED METHODOLOGY plus COMPARABILITY INFORMATION on:

• SAMPLING of CARBONACEOUS AEROSOLS on filters

• MEASUREMENT of:

TOTAL CARBON and ELEMENTAL CARBON CONCENTRATION

ABSORPTION COEFFICIENT

RESEARCH&DEVELOPMENT and INTEGRATION ACTIVITIES for ATMOSPHERIC MEASUREMENTS

within EUSAAR and ACTRIS EU-INTEGRATED INFRASTRUCTURES INITIATIVES (2006 – on going)

UNIQUE STUDY:

HIGHLY HARMONISED DATASET AT ALL SITES

A- DEVELOPMENT of a STANDARD method and ADOPTION

EUSAAR - ARTIFACT-FREE SAMPLING TRAIN Denuder efficiency from 40%-90% at different sites

1.1- DATA HARMONISATION: SAMPLING of CARBONACEOUS AEROSOLS

B- TESTS to assess SAMPLING ARTIFACT across the network, in winter and summer

Sampler 1TDQ

Sampler 2TQ

Sampler 3Q

Teflon filters

Quartz fiber filters

Front quartz filter

Denuder

Sampling Head

Carb

on h

oney

com

b m

onol

iths

Back-up filters

- HARMONISATION CORRECTIONS for POSITIVE ARTIFACT:

• Maximum average correction -30% for TC • no information for 3 sites

- NEGATIVE ARTIFACT NOT EXACERBATED BY DENUDER: <5%

A- DEVELOPMENT of a STANDARD method and ADOPTION

EUSAAR_2 protocol (CAVALLI et al., AMT 2010) for thermal-optical analysis

1.2- DATA HARMONISATION: ANALYSIS OF TOTAL, ORGANIC and ELEMENTAL CARBON

B- EXERCISES to assess INTER-LABORATORY COMPARABILITY within the NETWORK

Five inter-laboratory comparisons

- laboratory systematic BIASES and HARMONISATION FACTORS:

• max average deviation for EC/TC of 20% among sites using EUSAAR_2

• TC and EC with protocols other than EUSAAR_2 at two sites: max average deviation on EC/TC of a factor 2.3

1 2a 2b 3 6 7 8 12 13 16 17 25 26A

10A

18 E1 E2 E3

-4

-3

-2

-1

0

1

2

3

4

SPA-1 SPA-2HUN-1HUN-2ITA-1ITA-2

Laboratory

z-sc

ores

1.3- DATA HARMONISATION: MEASUREMENT of ABSORPTION COEFFICIENT

FILTER-BASED INSTRUMENTS :

• MAAP: MULTI ANGLE ABSORPTION PHOTOMETER (4)• PSAP: PARTICLE SOOT ABSORPTION PHOTOMETER (2)• AE: AETHALOMETER (2)

A- ADOPTION of STANDARDISED DATA CORRECTION PROCEDURES:

• MAAP: SHIFT OF THE OPERATIVE WAVELENGTH (MÜLLER et al., 2011) • PSAP: CORRECTION FOR RESPONSE TO ABSORPTION AND SCATTERING (BOND et al., 1999; OGREN, 2010)• AE: CORRECTION FOR MULTIPLE SCATTERING AND SHADOWING EFFECTS (WEINGARTNER et al., 2003)

- ADJUSTED OF ABSORPTION COEFFICIENT TO A COMMON WAVELENGTH 637 nm with constant Absorption Ångstrom Exponent of 1

B- WORKSHOPS to assess the INTER-INSTRUMENT COMPARABILITY within the NETWORK

- laboratory systematic BIASES and HARMONISATION FACTORS:

HFMAAP= 1 HFPSAP= 0.96-1.03 HFAE= 1.6

see Poster: Absorbing properties of BC over Europe, M. Zanatta

BIR MSY MLP OBK ISP0

2

4

6

8

10

12PM2.5

BIRASP

VHLHW

LPdD

MSYMLP ISP

FNK0

2

4

6

8

10

12PM10

BIR ASP VHL HWL MSY MLP ISP FNK0

5

10

15

20

25

30PM10

HARMONISED ANNUAL AVERAGE of PM MASS, TOTAL CARBON and ELEMENTAL CARBON

SIGNIFICANT POSITIVE GRADIENT from N to S6 μgm-3 (BIR) - 30 μgm-3 (ISP)

MAS

S μg

m-3

ELEM

ENTA

L C

AR

BO

NTO

TAL

CA

RB

ON

μg

m-3

BIR MSY MLP OBK ISP0

10

20

30

40

50

60PM2.5

• PM10 TOTAL CARBON and ELEMENTAL CARBON: SIGNIFICANT POSITIVE GRADIENT from N to S

TC: 1 μgm-3 (BIR) - 10 μgm-3 (ISP) EC: 0.1 μgm-3 (BIR) - 2 μgm-3 (ISP)

2.1 a,b RESULTS:

PdD high altitude site – special case!

NORTHWEST SOUTH

• PM10 Mass:

HARMONISED ANNUAL AVERAGE of ABSORPTION COEFFICIENT2.1 c RESULTS:

ABSO

RPTI

ON

CO

EFFI

CIEN

TM

m-1

• SIGNIFICANT POSITIVE GRADIENT from N to S: 0.8 Mm-1 (BIR) - 11 Mm-1 (ISP)

BIR VHL HWL PdD MSY MLP ISP FKL0

2

4

6

8

10

12PM10

2.2a RESULTS:

HARMONISED ANNUAL AVERAGE of TOTAL CARBON / MASS RATIO

LEAST CARBONACEOUS AEROSOL AT THE MEDITERRANEAN SITES, i.e. FINOKALIA and MONTSENY: 0.11 - 0.14

MOST CARBONACEOUS AEROSOL IN ISPRA: 0.30 - 0.40

FOR THE MAJORITY OF THE SITES, FAIRLY HOMOGENEOUS TOTAL CARBON / MASS RATIO: 0.16 - 0.24

BIR MSY MLP OBK ISP0.0

0.1

0.2

0.3

0.4

0.5PM2.5

BIR ASP VHL HWL MSY MLP ISP FNK0.0

0.1

0.2

0.3

0.4

0.5

0.6PM10

TOTA

L CA

RBO

N /

MAS

S

2.2b RESULTS:

HARMONISED ANNUAL AVERAGE of ELEMENTAL CARBON / TOTAL CARBON RATIO

FAIRLY HOMOGENEOUS (PUY DE DÔME EXCEPTED) ELEMENTAL CARBON / TOTAL CARBON RATIO: 0.12-0.23

ELEMENTAL CARBON / TOTAL CARBON RATIO DEPENDS ON THE PROXIMITY OF EMISSION SOURCES

BIR MSY MLP OBK ISP0.00

0.05

0.10

0.15

0.20

0.25

0.30PM2.5

BIR ASP VHLHWLPdD MSY MLP ISP FNK0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35PM10

ELEM

ENTA

L CA

RBO

N

/ TO

TAL

CARB

ON

2.2c RESULTS:

HARMONISED ANNUAL AVERAGE of ABSORPTION COEFFICIENT / ELEMENTAL CARBON, I.E. MASS ABSORPTION CROSS SECTION m2 g-1

MAC

m2 g

-1

BIR VHL HWL PdD MSY MLP ISP FKL0

2

4

6

8

10

12

14

16

18PM10

• HOMOGENEITY IN THE MAC VALUES: 6. 6 m2 g-1 (VHL) — 16.1 m2 g-1 (PdD) (PdD AND VHL HAVE A POORER DATA COVERAGE WITH LESS THAN 150 DATA POINTS)

• “EUROPEAN REGIONAL BACKGROUND” MAC = 10.8 ± 3.00

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50BIRASPVHLHWLMSYMLPISPFNK

HARMONISED SEASONAL AVERAGES of TOTAL CARBON / MASS RATIO

WIN

TER

SPRI

NG

SUM

MER

FALL

WIN

TER

SPRI

NG

SUM

MER

FALL

PM2.5 PM10

TOTA

L CA

RBO

N /

MAS

S

SEASON-SPECIFIC SOURCES OF CARBONACEOUS AEROSOL RESULT IN:

• MOST CARBONACEOUS AEROSOL IN WINTER-FALL DUE TO DOMESTIC HEATING (MORE EVIDENT AT CENTRAL SITES)

• BIOGENIC AEROSOL PEAKS IN SUMMER

• LEAST CARBONACEOUS AEROSOL IN SPRING AT ALL SITES BUT FINOKALIA

• INVERSE CYCLE AT FINOKALIA DUE TO AGRICULTURAL WASTE BURNING AND FOREST FIRES IN SPRING AND SUMMER

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

BIRMSYMLPISPOBK

2.3a RESULTS:

HARMONISED SEASONAL AVERAGES of ELEMENTAL CARBON / TOTAL CARBON RATIO

ELE

MEN

TAL

CARB

ON

/ TO

TAL

CARB

ON

WIN

TER

SPRI

NG

SUM

MER

FALL

WIN

TER

SPRI

NG

SUM

MER

FALL

PM2.5 PM10

ELEMENTAL CARBON / TOTAL CARBON RATIO SEASONAL CYCLE:

MAXIMUM IN FALL-WINTER (TRAFFIC + DOMESTIC HEATING) AND MINIMUM IN SUMMER (TRAFFIC + BIOGENIC SOURCES)

REMARKS:

- LESS PRONOUNCED CYCLE AT CONTINENTAL SITES DUE TO WEAKER BIOGENIC SOURCES

- AT FINOKALIA: MAXIMA IN SPRING-SUMMER DUE TO FIRES

- AT PUY DE DÔME: CYCLE DETERMINED MAINLY BY THE BOUNDARY LAYER DYNAMIC

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

BIRMSYMLPISPOBK

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30 BIRASPVHLHWLPdDMSYMLPISPFNK

2.3b RESULTS:

HARMONISED SEASONAL AVERAGES of ABSORPTION COEFFICIENT / ELEMENTAL CARBON, I.E. MASS ABSORPTION CROSS SECTION

WIN

TER

SPRI

NG

SUM

MER

FALL

MAC

m2 g

-1

MAC SEASONAL CYCLE:

- MAXIMUM IN SUMMER AT THE MAJORITY OF SITES

- IN CORRESPONDENCE TO THE MINIMUM OF THE EC/TC RATIO (I.E. MAXIMUM ABUNDANCE OF ORGANIC CARBON)

- THIS WOULD INDICATE AN AMPLIFICATION OF EC ABSORPTIVITY BY THE THICKER ORGANIC CARBON COATING

2.3c RESULTS:

0

2

4

6

8

10

12

14

16

18

20

BIR

HWL

PdD

MSY

MLP

ISP

FNK

3. CONCLUSIONSMETHODOLOGICAL

- IMPORTANCE OF COMMON STANDARDISED PROCEDURES FROM SAMPLING TO DATA SUBMISSION- THIS IS A MORE EFFICIENT AND ACCURATE APPROACH THAN APPLYING a-posteriori CORRECTION

FACTORS- PERIODICAL CHECKS OF COMPARABILITY

HIGHLY INTEGRATED NETWORK AND A BIAS-FREE DATASET ALLOW UNDERSTANDING SOURCES AND TRANSFORMATION OF AEROSOLS

PHENOMENOLOGICAL

ON A EUROPEAN REGIONAL BACKGROUND SCALE:

- CLEAR POSITIVE SPATIAL GRADIENT – FROM N TO S – FOR ALL EXTENSIVE AEROSOL PROPERTIES: PM MASS, TOTAL CARBON & ELEMENTAL CARBON AND ABSORPTION COEFFICIENT

- HOMOGENEITY FOR ALL INTENSIVE AEROSOL PROPERTIES: TOTAL CARBON / MASS, ELEMENTAL CARBON / TOTAL CARBON AND MAC - SEASONALITY OF INTENSIVE AEROSOL PROPERTIES AND SOURCES:

- TOTAL CARBON / MASS: MAXIMA IN FALL-WINTER (DOMESTIC HEATING) AND IN SUMMER (BIOGENIC AEROSOL)

- ELEMENTAL CARBON / TOTAL CARBON: MAXIMUM IN FALL-WINTER AND MINIMUM IN SUMMER- ABSORPTION COEFFICIENT / ELEMENTAL CARBON: MINIMUM IN FALL-WINTER AND MAXIMUM IN SUMMER