Probenahme und chemische Charakterisierung

von ultrafeinen Partikeln

Dominik van Pinxteren

Leibniz-Institut für Troposphärenforschung (TROPOS), Abteilung Chemie der Atmosphäre (ACD),

Leipzig

Motivation

PM as a health risk: Global burden of disease study

TOP 10

www.healthdata.org/gbd

PM as a health risk: Global burden of disease study

TOP 9

→ Fine and ultrafine particles pose a significant health riskeven in highly developed countries

Sampling methods

Sampling approaches for fine and ultrafine particles

Offline approach:1. Sample particles on substrate2. Analyse composition in lab

Online approach:Sample and analyse particles in one instrument

Pro: comprehensive compositionCon: long sampling times (hours – days)

Pro: short sampling times (sec – mins)Con: limited compositional information

Low pressure five-stage BERNER-impactor

aero

dynam

ic p

art

icle

dia

mete

r

[µm

]STAGE 1 50-140 nm

To the vacuum pump Sampling volume: 108 m³ in 24h

Sample collection: 5-stage Berner impactor

Sample collection on aluminum foils:

… which are chemically analysed.

Chemical analyses from impactor foils

Inorganic ions with ICWSOC with TOC analyzer

OC/EC with 2-step thermographic method

Metalswith TXRF

Alkanes, PAHs, Hopaneswith CPP-GC/MS

Size-resolved sampling of UFP

Micro Orifice Uniform Deposit Impactor(MOUDI):

Stage 1: 10 – 18 nm DpaerStage 2: 18 – 32 nm DpaerStage 3: 32 – 56 nm DpaerStage 4: 56 – 100 nm Dpaer

Stages 5-13: 0.18 – 18 µm Dpaer

Nano-MOUDI

5-Stage Berner Impactor:

Stage 1: 50 – 140 nm DpaerStage 2: 140 – 420 nm DpaerStage 3: 0.42 – 1.2 µm DpaerStage 4: 1.4 – 3.5 µm DpaerStage 5: 3.5 – 10 µm Dpaer

Impactor Sampling:

Challenges

Challenges in size-resolved sampling of UFP

nanoMOUDI gravimetric mass compared to expected mass based on numberconcentration measurement

0

5

10

15

20

25

30

35

40

0.001 0.01 0.1 1

Mobilitätsdurchmesser (µm)

dM

/dlo

gD

p (

µg

/m3)

DMPS

MOUDI

a)

0.0000001

0.000001

0.00001

0.0001

0.001

0.01

0.1

1

10

100

0.001 0.01 0.1 1

Mobilitätsdurchmesser (µm)d

M/d

log

Dp

(µ

g/m

3)

DMPS

MOUDI

b)

→ OK at first glance… …but it‘s not!

Challenges in size-resolved sampling of UFP

214.7

16.97.0

0.840.52 0.36 0.37 0.29

0.1

1

10

100

1000

1 2 3 4 5 6 7 8

Impaktorstufen

Masse M

OU

DI / M

asse D

MP

S

Nano-MOUDI

→ Severe overestimation of UFP mass, possibly due to „bounce-off“→Reasonable agreement from approx. 60 nm upwards

Mean (± 1σ) deviations of nanoMOUDI vs. DMPS mass for 29 samples

Size-resolved UFP chemical

composition

Street canyon samples comparison autumn vs. winter

Leipzig, Eisenbahnstrasse, street canyon, 10-stage Berner impactor

→ low, but measureable concentrations of ions, OC/EC + organics

Müller et al., 2012, doi: 10.1002/cite.201100208

Street canyon samples comparison weekday vs. weekend

→ Reasonable trends→ Absolute mass concentrations overestimated→ Absolute constituents concentrations might be correct

→ In the following: Berner impactor stage 1 (50-140 nm) as proxy for UFPs

mass EC

Leipzig ‚Aerosol 2013 - 2015‘ study:

Source apportionment of UFPs

Experimental approach

• 2 Campaigns(summer+winter 2013-2015)

• 4 Sampling sites in parallel

• 24h samples with 5-stage Berner impactor during 21 sampling daysper season

• Comprehensive chemicalcharacterisation

• Different source apportionmentapproaches

LMI: TrafficEIB: Traffic/Residential

TRO: UrbanMEL: Regional

van Pinxteren et al., 2016, doi: 10.1039/c5fd00228avan Pinxteren et al., Schriftenreihe LfULG, Heft 7/2016

PMF: Identified sources in all particle size ranges

Source Size range Main constituents Marker compounds

Traffic exhaustultrafinecoarse

WISCHopanes,

Sources in ultrafine particles (0.05 – 0.14 µm)

→ Traffic at traffic sites: ca. 0.2 – 1 µg m-3, 20 – 70 % of stage 1 mass (means)→ Photochem. at urban sites in summer: ca. 0.2 – 0.6 µg m-3, 20 – 50 → Solid fuel combustion in winter: ca. 0.2 – 0.9 µg m-3, 20 – 70 %

Impactor Stage 1

Su West Su East Wi West Wi East All

0.9

30

.93

0.9

30

.93

0.9

30

.93

0.7

50

.75

0.7

50

.75

0.7

50

.75

0.4

20

.42

0.4

20

.42

0.4

20

.42

0.0

92

0.0

92

0.0

92

0.0

92

0.0

92

0.0

92

41

13

30

13

17

37

36

22

57

14

39

17

301

.41

.41

.41

.41

.41

.4

1.4

1.4

1.4

1.4

1.4

1.4

0.7

80

.78

0.7

80

.78

0.7

80

.78

0.3

90

.39

0.3

90

.39

0.3

90

.39

21

20

44

11

15

39

28

27

10

50

30

11

50

1.5

1.5

1.5

1.5

1.5

1.5

0.9

0.9

0.9

0.9

0.9

0.9

0.5

70

.57

0.5

70

.57

0.5

70

.57

0.3

60

.36

0.3

60

.36

0.3

60

.36

49

28

16

29

24

29

11

10

29

12

39

21

24

37

17

0.9

40

.94

0.9

40

.94

0.9

40

.94

1.3

1.3

1.3

1.3

1.3

1.3

1.1

1.1

1.1

1.1

1.1

1.1

0.9

30

.93

0.9

30

.93

0.9

30

.93

31

40

28

18

34

12

23

46

19

12

38

30

19

1.2

1.2

1.2

1.2

1.2

1.2 1

1

1

1

1

1

0.6

60

.66

0.6

60

.66

0.6

60

.66

0.3

80

.38

0.3

80

.38

0.3

80

.38

34

21

15

17

21

14

19

19

21

19

13

30

28

15

26

30

22

0

25

50

75

100

0.05-0.14µm

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

Ma

ss

Fra

ctio

n%

Sources

Sea Salt

urban Dust

Spores

Cooking

Photochem.

Sec. Aer.

Biom. Comb.

Coal Comb.

Traffic

Tr. Exhaust

Approx. mean contributions to UFP mass at Leipzig-Mitte:50 % traffic20 % combustion20 % photochemistry10 % cooking

Source contributions in ultrafine, fine and coarse particles

Su West Su East Wi West Wi East All

0.9

30

.93

0.9

30

.93

0.9

30

.93

0.7

50

.75

0.7

50

.75

0.7

50

.75

0.4

20

.42

0.4

20

.42

0.4

20

.42

0.0

92

0.0

92

0.0

92

0.0

92

0.0

92

0.0

92

41

13

30

13

17

37

36

22

57

14

39

17

30

3.9

3.9

3.9

3.9

3.9

3.9

4.2

4.2

4.2

4.2

4.2

4.2

3.2

3.2

3.2

3.2

3.2

3.2

2.4

2.4

2.4

2.4

2.4

2.4

21

37

18

25

10

39

17

34

54

24

16

51

35 11

2.7

2.7

2.7

2.7

2.7

2.7

2.7

2.4

2.4

2.4

2.4

2.4

2.4

2.4

2.1

2.1

2.1

2.1

2.1

2.1

2.1

0.6

30

.63

0.6

30

.63

0.6

30

.63

0.6

3

13

34

10

12

27

24

12

17

34

19

23

41

39

34

22

1.4

1.4

1.4

1.4

1.4

1.4

1.4

1.4

1.4

1.4

1.4

1.4

0.7

80

.78

0.7

80

.78

0.7

80

.78

0.3

90

.39

0.3

90

.39

0.3

90

.39

21

20

44

11

15

39

28

27

10

50

30

11

50

4.9

4.9

4.9

4.9

4.9

4.9

5.2

5.2

5.2

5.2

5.2

5.2

4.1

4.1

4.1

4.1

4.1

4.1

2.4

2.4

2.4

2.4

2.4

2.4

21

14

33

29

16

27

47

11

20

48

17

14

57

20

2.1

2.1

2.1

2.1

2.1

2.1

2.1

1.9

1.9

1.9

1.9

1.9

1.9

1.9

1.6

1.6

1.6

1.6

1.6

1.6

1.6

0.2

40

.24

0.2

40

.24

0.2

40

.24

0.2

4

41

11

27

33

14

32

11

24

42 11

75

15

1.5

1.5

1.5

1.5

1.5

1.5

0.9

0.9

0.9

0.9

0.9

0.9

0.5

70

.57

0.5

70

.57

0.5

70

.57

0.3

60

.36

0.3

60

.36

0.3

60

.36

49

28

16

29

24

29

11

10

29 12

39

21

24

37

17

7.6

7.6

7.6

7.6

7.6

7.6 7

7

7

7

7

7

5.9

5.9

5.9

5.9

5.9

5.9

4.2

4.2

4.2

4.2

4.2

4.2

22

61 58

20 72

83

1.9

1.9

1.9

1.9

1.9

1.9

1.9

1.1

1.1

1.1

1.1

1.1

1.1

1.1

0.9

40

.94

0.9

40

.94

0.9

40

.94

0.9

4

0.3

30

.33

0.3

30

.33

0.3

30

.33

0.3

3

50

29

29

13

41

22 11 10

53

38

58

0.9

40

.94

0.9

40

.94

0.9

40

.94

1.3

1.3

1.3

1.3

1.3

1.3

1.1

1.1

1.1

1.1

1.1

1.1

0.9

30

.93

0.9

30

.93

0.9

30

.93

31

40

28

18

34

12

23

46

19

12

38

30

19

23

23

23

23

23

23

24

24

24

24

24

24

20

20

20

20

20

20

18

18

18

18

18

18

32

47 10

39

33

31

52

44

33

13

1.4

1.4

1.4

1.4

1.4

1.4

1.4

1.3

1.3

1.3

1.3

1.3

1.3

1.3

0.9

20

.92

0.9

20

.92

0.9

20

.92

0.9

2

0.5

10

.51

0.5

10

.51

0.5

10

.51

0.5

1

22

22

34

14

21

28

25

18

31

44

18

46

38

1.2

1.2

1.2

1.2

1.2

1.2 1

1

1

1

1

1

0.6

60

.66

0.6

60

.66

0.6

60

.66

0.3

80

.38

0.3

80

.38

0.3

80

.38

34

21

15

17

21

14

19

19

21

19

13

30

28

15

26

30

22

9.4

9.4

9.4

9.4

9.4

9.4

9.8

9.8

9.8

9.8

9.8

9.8

8.1

8.1

8.1

8.1

8.1

8.1

6.5

6.5

6.5

6.5

6.5

6.5

13

14

50 10

18

39 10

19

14

57

13

22

51

16

2

2

2

2

2

2

2

1.6

1.6

1.6

1.6

1.6

1.6

1.6

1.4

1.4

1.4

1.4

1.4

1.4

1.4

0.4

10

.41

0.4

10

.41

0.4

10

.41

0.4

1

10

40

22

28

10

13

27

10

16 11

18

34

20

18

24

27

0

25

50

75

100

0

25

50

75

100

0

25

50

75

100

0.05-0.14µm

0.42-1.2µm

3.5-10µm

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

LM

I

EIB

TR

O

ME

L

Ma

ss

Fra

ctio

n%

Sources

Sea Salt

urban Dust

Spores

Cooking

Photochem.

Sec. Aer.

Biom. Comb.

Coal Comb.

Traffic

Tr. Exhaust

→ Very different source contributions in different particle size ranges

UFP

Fine

Coarse

UFP source contributions

from airports?

UFP from jet engines

Fushimi et al., 2019: nanoMOUDI sampling @ Narita International, Japan (doi: 10.5194/acp-19-6389-2019)

Chemical analysis with TD-GC/MS identifies strong contribution of jetlubrication oils to aircraft exhaust UFPs

UFP size range

Summary

Zusammenfassung

• UFP Probenahme ist problematisch, v.a. für Partikel < 70 nm

• UFP Gesamtmasse wird von kohlenstoffhaltigem Material dominiert

• Hohe Anteile toxischer Bestandteile wie PAK (polyzyklische aromatische Kohlenwasserstoffe) und Metalle

• Hauptquellen:• Verkehr (Abgas und Nicht-Abgas)• Feststoffverbrennung (Winter)• Photochemie (Sommer)

→ Die chemische Zusammensetzung kann zur Identifizierung von UFP-Quellen verwendet werden

55.0%30.0%

15.0%

40.0%

5.0%

45.0%

10.0%

80.0%

15.0%2.5%2.5%

20.0%

30.0%40.0%

5.0%5.0%

Summer West Summer East

Winter West Winter East

Source categoryTrafficCoal.Comb.Biomass.Comb.SecondaryCooking

LMI UFP CompositionUFP Zusammensetzung in Leipzig-Mitte

Vielen Dank für ihre Aufmerksamkeit

Annex

Source Apportionment in Leipzig:

Lenschow Approach

Source apportionment approaches I: Lenschow

Lenschow et al., 2001: PM as superposition of sources in different regions

Traffic increment = c(LMI, EIB) - c(TRO)

Urban background increment = c(TRO) - c(MEL)

Regional background = c(MEL)

LMI, EIB

TRO

MEL

Summer Winter All

1.11.11.1 2.82.82.8 4.54.54.5 3.73.73.7 2.42.42.4

19

21

60

78

20

58

24

18

33

41

26

37

549.3

1.41.41.4 5.35.35.3 5.45.45.4 2.62.62.6 2.32.32.3

42

25

33

649.3

26

56

19

25

25

39

35

22

53

26

1.21.21.2 3.83.83.8 5.15.15.1 3.43.43.4 2.42.42.4

26

25

49

718.8

20

54

25

21

29

41

30

30

54

15

1.61.61.6 4.44.44.4 7.77.77.7 3.73.73.7 2.32.32.3

20

16

64

638.4

28

64 13

23

29

23

47

10

31

58

1.11.11.1 8.18.18.1 26 26 26 5 5 5 1.41.41.4

87

17

75

22

70 11

19

47

24

29

31

36

32

1.41.41.4 5.75.75.7 15 15 15 4.34.34.3 1.91.91.9

40

16

44

71

25

729.4

19

40

21

39

16

31

53

1.31.31.3 3.53.53.5 5.95.95.9 3.73.73.7 2.42.42.4

19

19

62

705.8

25

62

18

21

32

33

36

25

44

31

1.21.21.2 6.86.86.8 16 16 16 3.93.93.9 1.81.81.8

64

21 15

715.5

24

68 12

20

41

29

31

26

46

28

1.31.31.3 4.74.74.7 10 10 10 3.93.93.9 2.22.22.2

33

20

46

71 6

23

67 13

19

35

30

35

24

44

32

0

25

50

75

100

0

25

50

75

100

0

25

50

75

100

West

East

All

0.05-0.14µm

0.14-0.42µm

0.42-1.2µm

1.2-3.5µm

3.5-10µm

0.05-0.14µm

0.14-0.42µm

0.42-1.2µm

1.2-3.5µm

3.5-10µm

0.05-0.14µm

0.14-0.42µm

0.42-1.2µm

1.2-3.5µm

3.5-10µm

ma

ss

fra

ctio

n%

Increment

Traffic

Urban

Regional

Local vs. regional PM mass contributions at LMI site

LMI site Typical regional (transported) contributions:- 30% for ultrafines- 70% for accumulation mode

particles- 30% for coarse particles

Mean UFP source contributions:50 % traffic20 % urban background30 % regional background

→ 70 % reduction potential bylocal mitigation measures

van Pinxteren et al., 2016, doi: 10.1039/c5fd00228a