Samples analyzed (golden list + ):

SFU from IFUSP – 34 (fine + coarse modes)

MOUDI from IFUSP – 2 (9 stages)

HiVol from Gent – 22 (fine mode: front and back filters)

Ion Chromatography of Rondonia-2002 samples

Alla Falkovich, Gal Schkolnic and Yinon Rudich

Dept. of Environmental SciencesWeizmann Institute, Rehovot Israel

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0Minutes

1.01

1.25

1.50

1.75

2.00

uS

gly

ceri

cg

lyco

lic acet

ic

form

ic

MS

Ap

yru

vic

oxo

acet

icch

lori

de

nit

rite

nit

rate

adip

ic met

hyl

succ

inic

glu

tari

csu

ccin

icm

alic

carb

on

ate

mal

on

icm

alei

ch

ydro

xym

alo

nic

sulf

ate

oxa

licfu

mar

icaz

elai

c

syri

ng

icp

hth

alic va

nili

cp

ho

sph

ate

4-h

ydro

xyb

enzo

ic

citr

ictr

icar

bal

lalic

3-h

ydro

xyb

enzo

ic

MOUDI (from IFUSP)MDRO-39 st7 (0.33 – 0.56 um)

2 3 4 5 6 7Minutes

1.01

1.05

1.10

1.15

1.20

1.25

1.30

1.35

uS

gly

ceri

c (2

.261

)g

lyco

lic (

2.32

5)ac

etic

(2.

512)

form

ic (

3.25

4)

MS

A (

3.85

7)

pyr

uvi

c (4

.070

)

oxo

acet

ic (

5.87

9)

chlo

rid

e (6

.279

)

nit

rite

(6.

937)

19.0 19.5 20.0 20.51.35

1.40

1.45

1.50

1.55 uS

citr

ic (

19.5

70)

tric

arb

alla

lic (

19.8

57)

3-h

ydro

xyb

enzo

ic (

20.2

55)

14.5 15.0 15.5 16.0 16.5

1.30

1.40

uS

sulf

ate

(14.

52)

oxa

lic (

14.9

6)

fum

aric

(15

.20)

azel

aic

(15.

36)

15.6

8 ?

??

16.0 16.5 17.0 17.5 18.01.20

1.25

1.30

uS

syri

ng

ic (

16.1

59)

ph

thal

ic (

16.3

05)

van

ilic

(17.

001)

ph

osp

hat

e (1

7.22

5)

4-h

ydro

xyb

enzo

ic (

17.8

20)

13.0 13.5 14.0 14.5 15.0 Minutes

1.2

1.4

1.6

1.8

uS

adip

ic (

13.1

29)

met

hyl

succ

inic

(13

.188

)

glu

tari

c (1

3.27

3)su

ccin

ic (

13.4

30)

mal

ic (

13.4

94)

carb

on

ate

(13.

702)

mal

on

ic (

13.8

61)

mal

eic

(13.

987)

hyd

roxy

mal

on

ic (

14.2

40)

sulf

ate

(14.

523)

oxa

lic (

14.9

63)

fum

aric

(15

.197

)

azel

aic

(15.

363)

SFU (from IFUSP)

Anionic composition

0%

20%

40%

60%

80%

100%Tricarb

Ci

3hyBe

Cl

MSA

Va+4hyBe

Syr+Phth

Fo

Ac

DCA C4-6

Ox

NO3

SO4

Cationic composition

0%

20%

40%

60%

80%

100%Na

Mg

Ca

NH4+

K

SFU (from IFUSP)

Ion concentration

0500

10001500200025003000350040004500

9/12

N

9/14

D

9/14

N

9/15

D

9/17

D

9/17

N

9/18

D

9/18

N

9/19

D

9/19

N

9/23

D

9/23

N

9/24

N

9/25

D

9/25

N

10/3

N

10/4

D

10/4

N

10/5

D

10/1

6 N

10/1

8 D

10/1

8 N

10/2

4 D

10/2

4 N

10/2

6 D

10/2

6 N

10/3

0 N

11/1

D

11/1

N

11/3

D

11/3

N

11/6

N

11/7

D

11/1

0 N

Date

ng

/m3

NO3

SO4

Oxalic

NH4+

K

SFU (from IFUSP)– fine mode

Ion as a percent of total ionic mass

0.00

10.00

20.00

30.00

40.00

50.00

60.00

Date

NO3

SO4

Oxalic

NH4+

K

Ion as a percent of PM

0.00

2.00

4.00

6.00

8.00

10.00

12.00

14.00

Date

NO3

SO4

Oxalic

NH4+

K

NO3 SO4 Oxalic NH4+ K

Mean 4.2 42.6 7.4 12.1 14.1

Median 2.7 41.7 7.1 11.4 14.8

Min 0.0 25.7 1.4 5.9 6.2

Max 15.4 57.1 12.9 19.2 22.4

MOUDI (from IFUSP)

Dry period:

MDRO39 25-Sept-2002 Day

Transition period:

MDRO54 18-20-Oct-2002

An apparent coarse mode that contains Cl, NO3 and Ca

0.5 111 2 3 4 5 6 7 8 91010100.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60 PM Cl NO3 SO4 Ox DCA C

4-C

6

NH4 K Ca

C/(

Cto

tal d

log

Dp)

Dp (m)

0.5 111 2 3 4 5 6 7 8 91010100.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60 PM Cl NO3 SO4 Ox DCA C

4-C

6

NH4 K Ca

C/(

Cto

tal d

log

Dp)

Dp (m)

HiVol (from Ghent) – fine mode

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Dry Transition

Tricarballylic

Citric

Glyoxylic

3-hyBe

Cl

Syringic

Formic

Va+4-hyBe

Acetic

DCA C4-C6

Oxalic

NO3

SO4 0%

20%

40%

60%

80%

100%

Dry Transition

Mg

Na

Ca

NH4+

K

Ion concentration

0

1000

2000

3000

4000

5000

9/14

D

9/14

N

9/15

D

9/15

N

9/17

D

9/17

N

9/18

D

9/18

N

9/19

D

9/19

N

9/23

D

9/23

N

9/24

N

9/25

D

9/25

N

10/4

D

10/17

D

10/18

D

10/19

D

10/24

N

10/26

D

10/30

N

Date

ng

/m3

NO3

SO4

Oxalic

NH4+

K

Ion as a percent of total ionic mass

0

10

20

30

40

50

Date

Per

cen

t

NO3

SO4

Oxalic

NH4+

K

HiVol (from Ghent) – fine mode

NO3 SO4 Oxalic NH4+ K

Mean 4.2 42.6 7.4 12.1 14.1

Median 2.7 41.7 7.1 11.4 14.8

Min 0.0 25.7 1.4 5.9 6.2

Max 15.4 57.1 12.9 19.2 22.4

Mgy = 0.76x = 0.89

0102030405060708090

100

0 50 100 150

PIXI_IFUSP

IC_W

ISMg

y = 0.76x = 0.54

0102030405060708090

100

0 50 100 150

PIXI_IFUSP

IC_W

IS

COMPARISONs

SFU (IFUSP): IC (WIS) vs. PIXE (IFUSP), ng/m3

1.

Ky = 0.87x = 0.92

0200400600800

100012001400160018002000

0 500 1000 1500 2000

PIXI_IFUSP

IC _

WIS

Sy = 2.65x = 0.95

0

1000

2000

3000

4000

5000

6000

0 500 1000 1500 2000

PIXI_IFUSP

IC_W

IS

Cly = 0.97x = 0.46

0

20

40

60

80

100

120

0 20 40 60 80

PIXI_IFUSP

IC_W

IS

Without “zero”s

Ca analyzed by IC is

nine times higher than

that analyzed by PIXE.

What is the problem?

PIXE problem?

COMPARISONs – FINE fraction2.

SFU (IFUSP) – Brener (ISAC): IC (WIS vs ISAC)

Ion Slope Correlation coeff.

NO3 0.43 0.76

SO4 1.35 0.90

Oxalic 0.96

NH4 0.63 0.94

K 1.21 0.91

Ca 3.01 0.64

SFU (IFUSP) – HiVol (Ghent): IC (WIS

intralab)

Ion Slope Correlation coeff.

NO3 0.37 0.76

SO4 0.96 0.90

Oxalic 0.56 0.91

DCA C4-C6 0.63 0.85

Vanillic+4hyBe 0.79 0.72

NH4 0.88 0.94

K 0.83 0.91

HiVol (Ghent) – Brener (ISAC): IC (WIS vs

ISAC)

Ion Slope Correlation coeff.

NO3 1.03 0.92

SO4 1.15 0.84

Oxalic vs WSOC 0.87

NH4 0.59 0.85

K 1.28 0.87

Ca 0.27 0.34

Conclusions

1.

2.

3.