Shungo Kato, Yoshizumi Kajii

Tokyo Metropolitan University

CO, O3, and VOC results during 2004 Okinawa campaign

m aritim e(sum m er)

co ntin ental

O kin aw aO gasaw ara

R ishiri

Tokyo

120E 125E 130E 135E 140E115E

32N

27N

22N

36N

41N

45N

Russiabiomass burning

SE Asiabuiomass burnging

Moshiri

0

100

200

300

0

20

40

60

80

100

[CO

] (p

pbv)

[O3]

(pp

bv)

Aug Oct

Dec Feb

Apl

Jun

Aug

2001 2002

Okinawa

wintersummer summer

CO and O3 seasonal variation at Okinawa

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

1 2 3 4 5 6 7 8 9 10 11 12month

China

Korea

J apanPacific

SE Asia

Trajectory trend at Okinawa

Pollutant gas transport during winter

Okinawa - Ogasawara comparison

Okinawa (Hedo)

November,December 2000

Ogasawara (Chichi-jima)

December 1999

Dec-4 0405

Nov-18 1615

Nov-24 1150

14h

33h

66h

17N

27N

36N

41N

32N

22N

Okinawa

140E130E120E 135E125E115E

Ogasawara

Okinawa during winter in 2000

0

100

200

300

400

0

1000

2000

3000

[CO

] (p

pbv)

18-N

ov

22-N

ov

26-N

ov

30-N

ov

4-D

ec

[eth

ane]

, [ac

etyl

ene]

(pp

tv)

0 100 200 300 400 5000

1000

2000

3000

[eth

ane]

, [ac

etyl

ene]

(pp

tv) [Eta] = 6.9× [CO] +111

[Ace] = 4.7 × [CO] - 349

[CO] (ppbv)

0

100

200

300

400

0

20

40

60

[CO

] (p

pbv)

[O3]

(pp

bv)

CO

O320

-Nov

24-N

ov

28-N

ov

2-D

ec

6-D

ec

0 10 20 30 40 50 600

100

200

300

400

[O3] (ppbv)

[CO

] (p

pbv)

[CO] = -7× [O3] + 470

Ogasawara measurements

Ogasawara O3

0

10

20

30

40

50

60

70

ozon

e (p

pbv)

Aug

-97

Oct

-97

Dec

-97

Feb-

97

Apr

-98

Jun-

98

Aug

-98

0

400

800

1200

1600

2000

0

1

2

3

4

5

6

7

8

Dec

12

Dec

13

Dec

14

Dec

15

Dec

16

Dec

17

Dec

18

Dec

19

Dec

20

etha

ne [

ppt]

Tim

e fr

om th

e re

gion

[da

y]

ethane

Ogasawara 1999

0

1000

2000

3000Ethane

Okinawa[Eth

ane]

(pp

tv)

0

400

800

1200 Propane

[Pro

pane

] (p

ptv)

0 24 48 72 96 1200

200

400

Transport time from souce region 　 (hour)

Butane

Ogasawara

[But

ane]

(pp

tv)

Transport time and HC concentration at Okinawa and Ogasawara

December

Okinawa 2000

Ogasawara 1999

CO, O3, and VOC measurements during the 2004 spring campaign at Hedo

HgCO, O3HV

AMSNep

Okinawa island

Cape Hedo

CO, O3 instruments

CO : TEI model 48C

Infrared absorption

O3 : TEI model 49

UV absorption

O3zero

CO

outside

(Pt)

filter

trap

HEDO daily average

0

100

200

300

400

500

600

700

10-M

ar

9-A

pr

9-M

ay8-

Jun

8-Ju

l

7-A

ug

6-S

ep

6-O

ct

5-N

ov5-

Dec

4-Ja

n

3-Fe

b

5-M

ar

4-A

pr

4-M

ay3-

Jun

3-Ju

l

2-A

ug

1-S

ep

1-O

ct31

-Oct

30-N

ov

30-D

ec

29-J

an

28-F

eb

30-M

ar29

-Apr

29-M

ay

28-J

un

28-J

ul

27-A

ug

26-S

ep26

-Oct

25-N

ov

25-D

ec

24-J

an

23-F

eb

24-M

ar23

-Apr

23-M

ay

22-J

un

CO

(pp

bv)

0

10

20

30

40

50

60

70

80

O3

(ppb

v)

COO3

Seasonal variation of CO and O3 at HEDO

winter winter winter

summer summer summer

Hedo 2004 spring CO- O3

0

100

200

300

400

500

600

700

800

21-M

ar

22-M

ar

23-M

ar

24-M

ar

25-M

ar

26-M

ar

27-M

ar

28-M

ar

29-M

ar

30-M

ar

31-M

ar

1-A

pr

2-A

pr

3-A

pr

4-A

pr

5-A

pr

6-A

pr

7-A

pr

8-A

pr

9-A

pr

10-A

pr

11-A

pr

12-A

pr

13-A

pr

14-A

pr

15-A

pr

16-A

pr

17-A

pr

18-A

pr

19-A

pr

20-A

pr

21-A

pr

22-A

pr

23-A

pr

24-A

pr

25-A

pr

26-A

pr

27-A

pr

28-A

pr

29-A

pr

30-A

pr

1-M

ay

2-M

ay

3-M

ay

CO

(pp

b)

0

10

20

30

40

50

60

70

80

O3

(ppb

)

CO (std cor)O3

CO and O3 during Hedo campaign

Short span change Long span change

China Korea Japan

0.0

50.0

100.0

150.0

200.0

250.0

300.0

350.0

400.0

18-M

ar19

-Mar

20-M

ar21

-Mar

22-M

ar23

-Mar

24-M

ar25

-Mar

26-M

ar27

-Mar

28-M

ar29

-Mar

30-M

ar31

-Mar

1-A

pr2-

Apr

3-A

pr4-

Apr

5-A

pr6-

Apr

7-A

pr8-

Apr

9-A

pr10

-Apr

11-A

pr12

-Apr

13-A

pr14

-Apr

15-A

pr16

-Apr

17-A

pr18

-Apr

19-A

pr20

-Apr

21-A

pr22

-Apr

23-A

pr24

-Apr

25-A

pr26

-Apr

27-A

pr28

-Apr

29-A

pr30

-Apr

1-M

ay2-

May

3-M

ay4-

May

5-M

ay6-

May

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

CO (std cor)trj- new

China

Korea

Japan

marine

CO and air mass origin

Hedo 2004 spring CO- O3

0

100

200

300

400

500

600

700

80021

-Mar

22-M

ar

23-M

ar

24-M

ar

25-M

ar

26-M

ar

27-M

ar

28-M

ar

29-M

ar

30-M

ar

31-M

ar

1-A

pr

2-A

pr

3-A

pr

4-A

pr

5-A

pr

6-A

pr

7-A

pr

8-A

pr

9-A

pr

10-A

pr

11-A

pr

12-A

pr

13-A

pr

14-A

pr

15-A

pr

16-A

pr

17-A

pr

18-A

pr

19-A

pr

20-A

pr

21-A

pr

22-A

pr

23-A

pr

24-A

pr

25-A

pr

26-A

pr

27-A

pr

28-A

pr

29-A

pr

30-A

pr

1-M

ay

2-M

ay

3-M

ay

CO

(pp

b)

0

10

20

30

40

50

60

70

80

O3

(ppb

)

CO (std cor)O3

1 2 3 4 5 6KCJ J C KJ CKJ

High O3High CO

0

10

20

30

40

50

60

70

80

0 50 100 150 200 250 300 350 400

CO (ppb)

O3

(ppb

)

O3- 1O3- 2O3- 3O3- 4O3- 5O3- 6

CO - O3 correlation plot

VOC measurements

Canister sampling ; every 2 days, total 21 samples

Analyzed by concentrator + GC-FID or GC-MS

Analyzed species

Alkane

ethane

propane

butane

pentane

hexane

...

Alkene

ethylene

propylene

…

acetylene

Aromatics

benzene

toluene

xylenes

...

Halocarbon

CH3Cl

CH3Br

C2Cl4

CH2Cl2

...

Others

DMS

(CH3CN)

(acetone)

(CH3CHO)

(CH3OH)

...

1

10

100

1000 ethane

propane

n-pentane

n-butane

acetylene

conc

entr

atio

n (p

ptv)

22-M

ar

27-M

ar

1-A

pr

6-A

pr

11-A

pr

16-A

pr

21-A

pr

26-A

pr

1-M

ay

500

1000

5

10

15

ethylene

C2Cl4

benzene

acetylene

conc

entr

atio

n (p

ptv)

22-M

ar

27-M

ar

1-A

pr

6-A

pr

11-A

pr

16-A

pr

21-A

pr

26-A

pr

1-M

ay

10

20

30

40

50

60

50

100

150

200

CHCl3

C2Cl4

C2H4Cl2CH2Cl2

conc

entr

atio

n (p

ptv)

22-M

ar

27-M

ar

1-A

pr

6-A

pr

11-A

pr

16-A

pr

21-A

pr

26-A

pr

1-M

ay

1000

2000

3000

4000

10

20

30

40

CH3CHO CH3CN

acetone

CH3OH

conc

entr

atio

n (p

ptv)

22-M

ar

27-M

ar

1-A

pr

6-A

pr

11-A

pr

16-A

pr

21-A

pr

26-A

pr

1-M

ay

VOC concentration changes

0 500 10000

1000

2000

acetylene (pptv)

conc

entr

atio

n (p

ptv)

ethane

propane

y= 1.68X + 714

y= 0.88x + 31

0 500 10000

10

20

30

acetylene (pptv)

conc

entr

atio

n (p

ptv)

C2Cl4

CH3CN

y= 0.0072X + 3.7

y= 0.014x +10.5

Correlation between acetylene

Acetylene : indicator of combustion

Anthropogenic VOC :

good correlation between acetylene

C2Cl4 : urban indicator

CH3CN : biomass burning indicator

also urban source ?

0 500 10000

200

400

600

800

0

10

20

30

40

50

acetylene (pptv)

conc

entr

atio

n (p

ptv)

CH3Br

CH3Cl

Correlation between acetylene

CH3Cl, CH3Br :

biomass burning indicator

plants and ocean sources

Hedo 2004

0

10

20

30

40

50

0 500 1000

CH3Cl (ppb)

CH3C

N (-

)

CH3CN

Hedo 2004

0

10

20

30

40

50

0 10 20 30 40

CH3Br (ppb)

CH3C

N (-

)

CH3CN

0 500 10000

1000

2000

acetylene (pptv)

conc

entr

atio

n (p

ptv)

CH3CHO

acetone

y= 0.32X + 1269

y= 0.44x +1785

Acetone :

slightly higher in polluted air

CH3CHO :

local photochemistry

Hedo 2004 TMU

0.0

50.0

100.0

150.0

200.0

250.0

300.0

350.0

400.0

450.0

500.0

21-M

ar22

-Mar

23-M

ar24

-Mar

25-M

ar26

-Mar

27-M

ar28

-Mar

29-M

ar30

-Mar

31-M

ar1-

Apr

2-A

pr3-

Apr

4-A

pr5-

Apr

6-A

pr7-

Apr

8-A

pr9-

Apr

10-A

pr11

-Apr

12-A

pr13

-Apr

14-A

pr15

-Apr

16-A

pr17

-Apr

18-A

pr19

-Apr

20-A

pr21

-Apr

22-A

pr23

-Apr

24-A

pr25

-Apr

26-A

pr27

-Apr

28-A

pr29

-Apr

30-A

pr1-

May

2-M

ay3-

May

J ST

CO

(pp

bv)

0

200

400

600

800

1000

1200

acet

ylen

e (p

ptv)

CO (ppb)Acetylene

Hedo 2004 TMU

0.0

50.0

100.0

150.0

200.0

250.0

300.0

350.0

400.0

450.0

500.0

21-M

ar22

-Mar

23-M

ar24

-Mar

25-M

ar26

-Mar

27-M

ar28

-Mar

29-M

ar30

-Mar

31-M

ar1-

Apr

2-A

pr3-

Apr

4-A

pr5-

Apr

6-A

pr7-

Apr

8-A

pr9-

Apr

10-A

pr11

-Apr

12-A

pr13

-Apr

14-A

pr15

-Apr

16-A

pr17

-Apr

18-A

pr19

-Apr

20-A

pr21

-Apr

22-A

pr23

-Apr

24-A

pr25

-Apr

26-A

pr27

-Apr

28-A

pr29

-Apr

30-A

pr1-

May

2-M

ay3-

May

J ST

CO

(pp

bv)

0

2

4

6

8

10

12

14

C2C

l4 (

pptv

)

CO (ppb)CCl2CCl2

CO, acetylene, C2Cl4

acetylene C2Cl4