[PPT] - as organic matter e d l v s o d i s h h i g a - u l PowerPoint Presentation

SLIDE 1

S t r u c t u r e

and

reactivity

f

d i s s

l

v e d

rganic matter

as

determined by

u l t r a

h

i g h

resolution

electrospray

i

n

i z a t i

n

mass s p e c t r

m

e t r y

S u n g h w a n

Kim Adviser:

P a t r i c k

G.

h a t c h e r

Department

f

Chemistry, The Ohio State University, C

l

u m b u s , OH

43210

SLIDE 2

O v e r v i e w

Understanding

f

t h e r i v e r i n e d i s s

l

v e d organic matter ( D O M )

is

i m p

r

t a n t however l i t t l e

is

known a b

u

t t h i s material

in a

molecular

l e v e l .

R i v e r i n e D O M

is

a

major source

f

c a r b

n

f l

w

to

t h e

ceans and plays

a n

i m p

r

t a n t role

i n the

global cycle

f

carbon.

SLIDE 3

A

riddle

in a

g l

b

a l

c a r b

n

cycle

0.3 Gt of carbon is large

enough to sustain the turnover

f the entire ocean
However, a little resemblance

was found between two carbon pools.

Low amount of lignin phenol

(terrestrial bio-marker) exists in

ceanic DOC pool.
6

13

C

isotope signatures are different.

(units: Gt)

Adapted from Houghton et. al. Climate change 1994 (1995), Cambridge Press, New York

* Meyers-Schuttle & Hedges, Nature (1986), 321, 61-63

SLIDE 4

I s

l

a t i

n
f

DOM

from

natural river

w a t e r

samples

SLIDE 5

How

to

isolate the

DOM?

N

Final elution i n c l u d e s a l t

—

d i a l y s i s n e c e s s a r y

X A D

extraction

Established method L a r g e volume

f

chemical F r a c t i

n

a t i

n

L a r g e amount

f

s a m p l e

Ultrafiltration

possible Requires instrument Takes

a

l

n

g time

Freezedrying

Not-selective Concentrate salts too

SLIDE 6

H

w

t

isolate DOM from

river water?

Disk

type

C

18

solid

p h a s e

extraction

Benefits

1.

F a s t e r e x t r a c t i

n

2.

S i m p l e

experiment setup

3.

easily handle s m a l l

amount

f

sample Questions to be answered

1 .

Retention rate?

2.

D

e

s

c

l

l e c t e d sample reflect

DOM

in

r i v e r ?

L

u

c h

u

a r n ,

P.; Opsahl, S.; Benner, R.;(2000), Anal. C h e m . 72, 2780-2787

SLIDE 7

Retention rate?

Retention rate of

70 %

0.8 0.4

eluent

0-

250 300 350 400 450 500 Wavelength (nm)

SLIDE 8

Does final eluent reflect the

DOM in river?

H2O

DOM acquired

\J

by freeze drying

CH

3

OH

DOM acquired

by SPE

Ipp1n

I

SLIDE 9

E S I

M

S

data

n

D O M

(quadrupole time

f

flight mass spectrometry)

M S

spectrum from control

( u l t r a

h

i g h purity w a t e r p r

c

e s s e d with same p r

c

e d u r e )

M S

s p e c t r u m from D O M i s

l

a t e d b y

C

18

SDE

. n h 1 1 r I l

s

. I . , J l T . n

ia

M / z

2

200 aa 800

1

l2

1 4

1600
2000

912 313

1

0 -r.---

I

300

SLIDE 10

S p e c t r u m

f

D O M

f r

m

Rio

TempisquitO at

Costa

R i c a

2000

q37 050

l0

218 4 344) Sm(SG

23

) , 011(37323) 3 1 . 1 8 6 149051 347.199375 224 .A03.233 ..417.251 2 8 9 . 1 9 7 I 433257 287.191k

IIi

iI 219.163

N

I N

1 _

SLIDE 11

High resolution mass spectrum

Resolution “ 80,000

_

dê âk&M

_

384 388 392 396

SLIDE 12

2D

N M R

( T O C S Y )

d a t a

n

D O M

Sample by freezedrying Sample by

C

18

SDE

2.%?4

_

3

p m

6 5 3 2

1

(1)

a r

m

a t i c s ; (2) s u g a r s ; aliphatic units

bridging

lignin

aromatics; amino acids

(a-13

couplings); (3) methylene units

adjacent

to

ethers, e s t e r s , and

hydroxyls

in

aliphatic chains; amino acids

(a-3-’y

couplings); (4) methylene

in

aliphatic chains; and methyl units

in

amino acids and aliphatic chains.

SLIDE 13

Conclusion

1

.

D O M c a n b e e x t r a c t e d w i t h

C

18

s

l

i d p h a s e d i s k e x t r a c t i

n

i n

a

s h

r

t e r t i m e w i t h s i m p l e e q u i p m e n t .

2.

Extracted D O M w a s successfully analyzed by high resolution ESI-MS resulting high resolution

spectra.

Sunghwan Kim

et.

a! submitted

to O r g a n i c G e

c

h e m i s t r y

SLIDE 14

R e s

l

v i n g p

w

e r is v e r y

critical

100

1 — Q

T

O F analysis

f

D O M

Reso’ving power

— 1 ,

I

agi

7

T

FT-ICR analysis

f

D O M

Resolving power

—80,000

I,

r

390.3 390.5 390.7 390.9 3 9 1 . 1 391.3 391.5 391.7

SLIDE 15

U l t r a

h

i g h resolution spectrum

f

DOM

14

8

10 6 91 4

I

23

7

j r

UJIiAiL

1

Resolving power 200,000

17 18 1 3

1

2A

L J

1 5 16

A

469 074 469 115 469 156

III

P r

p
s

e d m

l

e c u l a r T h e

r

e t i c a l D i f f e r e n c e from P e a k # O b s e r v e d v a l u e s f

r

m u l a v a l u e s T h e

r

e t i c a l v a l u e ( p p m )

I

C

25

H

10 10

469.02018 4 6 9 . 2 1 2

.

1 2

C

2 2

H

1 4 1 2

4 6 9 . 4 1 1 8 4 6 9 . 4 1 2 5

0.1

3

C

26

H

14

9

4 6 9 . 5 6 4 6 469.05651 0.1 4

C

23

H

18 11

4 6 9 . 7 7 6 3 4 6 9 . 7 7 6 4

S

C

27

H

18

5

4 6 9 . 9 2 8 8 4 6 9 . 9 2 8 9

6

C

24

H

22 10

4 6 9 . 1 1 4 1 4 6 9 . 1 1 4 2

7

C

28

H

22

7

4 6 9 . 1 2 9 3 4 6 9 . 1 2 9 2 8

8

C

25

H

26

9

4 6 9 . 1 5 4 2 4 6 9 . 1 5 4 1

9

C

29

H

26

O

6

4 6 9 . 1 6 5 7 6 4 6 9 . 1 6 5 6 6

.

2 1

C

22

H

30 11

4 6 9 . 1 7 1 5 1 4 6 9 . 1 7 1 5 4 . 1

11

C

26

H

30

8

4 6 9 . 1 8 6 8 1 4 6 9 . 1 8 6 7 9

12

C

30

H

30

5

4 6 9 . 2 2 1 4 6 9 . 2 2 5 . 1

13

C

23

H

34 10

4 6 9 . 2 7 8 9 4 6 9 . 2 7 9 2

. 1 1 4

C

27

H

34

7

4 6 9 . 2 2 3 1 6 4 6 9 . 2 2 3 1 8

15

C

31

H

34

4

4 6 9 . 2 3 8 3 8 4 6 9 . 2 3 8 4 3

. 1 16

C

24

H

38

9

4 6 9 . 2 4 4 2 3 4 6 9 . 2 4 4 3 1 . 2

1 7

C

28

H

38

6

4 6 9 . 2 5 9 4 9 4 6 9 . 2 5 9 5 6 . 2

18

C

29

H

42

5

469.29584 4 6 9 . 2 9 5 9 5 . 2

m l z

SLIDE 16

9.4 T FT-ICR at NHMFL

SLIDE 17

Trees or forest?

14

8

17 2 6

12J

469.033 469.074 469.115 469.156 469.197 469.238 469.279

mlz

II,’,

I.. Ii

SLIDE 18

Graphical

s

t a t i s t i c a l m e t h

d

f

r

the study

f

s t r u c t u r e and reaction processes

f

coal

D. W. VAN KREVELEN, D . S c . , M.A.I.Ch.E.

A

graphical-statistical method is developed for t h e study

f

problems connected with structure and reaction p r

c

e s s e s

f coal.

in

this method use is made of a diagram in which t h e atomic hydrogen-to-carbon ratio has been plotted v e r s u s the atomic oxygen-to-carbon r a t i

.

T h i s graphical method

ffers the

advantage that the principal reactions s u c h as decarboxylarion, demeihanation, dehydration, dehydrogenation, hydrogenation and

xidation

in the aforementioned diagram can b e represented by straight lines. Furthermore, an auxiliary diagram is used where the hydrogen-to-carbon ratio

f

hydrocarbons has been

pltted

as a f u n c t i

n of

t h e number

f

carbon atoms per molecule. From

a

combination

f

t h e two diagrams valuable information can be drawn as regards the structure of

xygen containing
rganic products

e . g . high p

l

y m e r s , s u c h as cellulose. These ideas are applied to the codification series. T h e skeleton structure

f

l i g n i n evolved in the literature proves to be in conformity with the results

f the graphical statistical method.

The conversion

f lignite

to bituminous c

a

l is found to b e based on a decarboxylation: t h e conversion from high rank bituminous coal to anthracite i s a reaction process in which methane is removed almost exclusively in t h e transition f r

m

low

rank to high rank bituminous coal a decarboxylation as

well as a demethanarion

and a dehydration

ccur.

The stoichiometry of t h e coalification is expressed in f

r

m u l a e .

A

correlation is made between the coalifica non

f

various vegetable components a n d t h e rank

f

coal in which the product formed cannot be d i s t i n g u i s h e d from vitrain. Finally t h e formation process

f

fusain is studied in more detail and t h i s leads to the

con

struction

f

a f u s i n i z a f i

n

band by t h e side

f

t h e coal band

( =

vitrinization band). T h e p r i n c i p a l reaction processes

f coal,

namely carbonization, hydroconversion, solvent extraction, hydrogenolysis and

x

i d a t i

n

, are investigated b y a graphical-statistical method.

it

proves that both in carbonization and in

xidation

with gaseous

xygen all coalification

products show a t e n d e n c y

to yield

a uniform

final product; in the

c a r b

n

i z a tion this product has the composition

(C

1

H

2

.

1

j.

in the case of

xidation

t h e composition i s

(C

5

H

2 3

)

1

.

F u r t h e r carbonization results in a graphirization,

while an oxidation beyond the above c

m

p

s

i t i

n

gives

a complete conversion to carbon dioxide and

water. Thermal decomposition in the presence

f

w a t e r vapour under pressure must b e based

n

a

reaction mechanism which

s

J

s

d y

related with the codification. I n hydrogenation t h e character of t h e final products depends b

t

h

n

t h e character of the starring material and

n the

conditions under which t h e hydrogenation is carried

ut.

In oxidation with nitric acid, two stages can be distinguished: in the first stage hydrogen is removed while

xygen

is absorbed, in t h e second stage both hydrogen

a n d

x

y g e n are absorbed a n d this in t h e approximate proportion

f

1:

1 .

Solvent extraction of coal shows that coal is not

a

homogeneous macromolecule: there is either a differentiation in molecular size

r

such a configuration that fragments

f

a r e l a t i v e l y low molecular weight a r e split

ff

rather

easily.

van Krevelen,

D . W .

(1950) Fuel 29, 269-284

SLIDE 19

van Krevelen plot: An informative graphical method for a n a l y s i s

f

u l t r a h i g h

r

e s

l

u t i

n

b r

a

d b a n d

spectra

f natural organic matter

A visual tool to study complicated s p e c t r a .

SLIDE 20

I

I...

E

van Krevelen Plot

2

1.5

1

. 5

t

.

p e a k O b s e r v e d Proposed A t

m

i c ratio A t

m

i c r a t i

number

v a l u e molecular

f

H/C

f 0/C

1

469.02018

C

2 5

H

1 1

. 4 . 4

2

469.04118

C

2 2

H

1 4 1 2

. 6 4 . 5 5

3

469.05646

C

2

H

1 4 1 2

. 5 4 . 4 6

4

4 6 9 . 7 7 6 3

C

23

H

18 11

. 7 8 . 4 8

5

469.09288

C

27

H

18

8

. 6 7 . 3

6

469.11401

C

24

H

22 10

. 9 2 . 4 2

7

4 6 9 . 1 2 9 3

C

28

H

22

7

. 7 9 . 2 5

8

469.15042

C

25

H

26

O

9

1 . 4 . 3 6 9

4 6 9 . 1 6 5 7 6

C

29

H

26

6

. 9 . 2 1

10

469.17151

C

22

H

30 11

1.36 . 5

11

469.18681

C

26

H

30

8

1.15 . 3 1 1 2

469.20201

C

30

H

30

8

1 . . 2 7

13

469.20789

C

2 3

H

3 4 1

1.48 . 4 3 14

469.22316

C

27

H

34

7

1 . 2 6 . 2 6

15

469.23838

C

31

H

34

O

4

1 . 1 . 1 3 16 469.24423

C

24

H

38

9

1 . 5 8 . 3 8 1 7

469.25949

C

28

H

38

6

1.36 0.21

1 8

4 6 9 . 2 9 5 8 4

C

2 9

H

4 2

5

1 . 4 5 0.17

. 5

Ic

Atomic ratio of

SLIDE 21

2-

1.5

C-)

I

‘4-

I

C.)

E

0.5 0.0

van Krevelen Plot of DOM

0.5 Atomic ratio of 0/C

SLIDE 22

van Krevelen plot

as a tool to

identify and display series of molecules possibly from v a r i

u

s

c h e m i c a l reactions

R e a c t i

n

C h a r a c t e r i s t i c

f

a line De-carboxylation p a s s (2,0) Hydration or dehydration s l

p

e

f

2

Oxidation horizontal line H y d r

g

e n a t i

n or

d e h y d r

g

e n a t i

n

vertical line

x

i d a t i

n alcohol

t

a

l d e h y d e slope

f
2
x

i d a t i

n
f

alcohol to acid slope

f
1

Addition

f

CH

2

p a s s (0,2)

SLIDE 23

C

6 H

10

2

t

‘C

7 H

12

2 C

8 H

1 4

2

C H

2

0/C

ratio

CH

2

2-

1 —

Reaction Characteristic

f

a line De-carboxylation pass (2,0) Hydration or dehydration slope

f

2

Oxidation horizontal line Hydrogenation or dehydrogenation vertical line

xidation alcohol to aldehyde

slope

f
2
xidation
f

alcohol to acid slope

f
1

Addition

f

C H

2

pass (0,2)

SLIDE 24

v a n Krevelen p l

t as

a tool to identify and

display series of molecules possibly from various chemical reactions

2

H

2

. C.)

.

. .

.

I

H

2

1.5

.

II—

.

l

w . . . .

6

.

C.)
.

, :

I

. .

—

—a.——

4

J f

I

. 5

.

C H

2

CH

2

.

. 5 Atomic r a t i

f

OIC

SLIDE 25

van K r e v e l e n plot

as a

tool to identify and display series

f

m

l

e c u l e s

f r

m

v a r i

u

s c h e m i c a l reactions

2

H

2

1.5

:
I
Ii

/•.•

O

J

q

,

4

4 Cu

I

I-

E

lkiC4

L

S..
‘

I . —

CH

2

O

. 5

CH

2

0.0 0.5 Atomic

r a t i

f

OIC

SLIDE 26

Kendrick mass defect analysis* on

C H

2

s e r i e s

f

p e a k s

A possible reaction

H Kendrick

mass

(CH

2

)

O H

Cl

C.)

G) U)

C l ) Ce

E

C.)

I

V

G)

0.70

1

0.60

0.50
0.40
0.30
0.20

0.10

0.00

4

replacing

2 H b y O

. . . . . . . . . . . . . . .

K

.

.

.
.
.
.
.
.
.
.
.
.
s

e r i e s

CH

2

300 4 500 600 700

OMe

*

Kendrick, E., Anal.

Chem,

35,

2

146-2154 (1963)

SLIDE 27

Bio-markers have their own specific elemental composition

vK plot allows us to do qualitative visual analysis on complicated mass spectrum

— analogy to 1D NMR

2.5

lipid

____

cellulose

2

protein

C..)

1.5

condensed

igin

hydrocarbon

V...

.....

. ...... .

E

1

0.5 0.0 0.5 Atomic ratio of O!C 1.0 1.5

SLIDE 28

Bio-markers have their own specific elemental composition

vK plot allows us to do qualitative visual analysis on complicated mass spectrum

— analogy to 1D NMR

2.5

coo H

lipid

____

cellulose

2

jJ

protein

15

30

2

—O/CO1 H/C2

S 1.5

condensed

lignin

— —

hydrocarbon

E

1

0.5 0.0 0.5 Atomic ratio of 0/C 1.0 1.5

SLIDE 29

Bio-markers have their own specific elemental composition

vK plot allows us to do qualitative visual analysis on complicated mass spectrum

— analogy to 1D NMR

protein

C)

(U

C.)

E

2.5 2 1.5

1

O.5• lipid

condensed hydrocarbon cellulose

lignin

C

6 H

12

6

O/C 1,H/C2

I

0.0 0.5 Atomic ratio of 0/C 1.0 1.5

SLIDE 30

Bio-markers have their own specific elemental composition

vK plot allows us to do qualitative visual analysis on complicated mass spectrum

— analogy to 1D NMR

OH

cellulose

OMe

OH

C.)

I

C.,

E

2.5 2 1.5

I

0.5

lipid

protein

condensed hydrocarbon

C

10

H

12

3

0/C

0.3, H/C

1.2

0.0 0.5 Atomic ratio of OIC 1.0 1.5

SLIDE 31

C)

I

E

4

condensed

/

lignin carbohydrate

. .: .

.

...

4
2-

1.5

1-

0.5

0.0

I

Ft

I

.q

.
.
0.5

Atomic ratio of 0/C

SLIDE 32

2D

NMR

data

n

D O M

Sample by

C

18 SDE _ _ _ _

H

2E

7 !

ppm

6 5 4 3 2

1

(1)

aromatics;

(2)

sugars;

a l i p h a t i c units b r i d g i n g

l i g n i n

aromatics; amino acids

( c t

3

couplings); (3) methylene units

a d j a c e n t t

e

t h e r s , esters, and

hydroxyls

in

aliphatic c h a i n s ; amino acids

(a-3-y

couplings); (4) methylene

in

a l i p h a t i c c h a i n s ; and methyl units

i n

amino acids and aliphatic chains.

SLIDE 33

3D vK plot —a visual tool to compare

multiple complex spectra

..

p2.5

15

I

°05

0.0

0.5 1.0

Aerial view display

0.0 0.5 1.0 1.5 2.5 2.0

I

1-

1.5

.4-

c

I

to

0.5 0.0 1.5

AtomiC ratio of 0/C

Atomic ratio of 0/C

SLIDE 34

3D vK plot —a visual tool to compare multiple

complex spectra

Cu

I

C)

E

DOM from McDonalds Branch

0.2 0.3 0.4 0.5 Atomic 0/C ratio

0.1

0.6 0.7

SLIDE 35

Existence

f

molecules

i n

samples

—

an c a r b

n

a n d

h y d r

g

e n deficient n a t u r a l

river

w a t e r

i m p l i c a t i

n

f

r

black black

carbon

cycle

SLIDE 36

Black

c a r b

n

(BC)

T

h e

b l a c k carbon

( B C )

is

byproduct

f

incomplete combustion p r

c

e s s e s .

B

C has

been s h

w

n

to

h a v e discemable influence on biogeochemical cycles, c l i m a t e c h a n g e , human health, f e r t i l i t y

f

s

i

l s , a n d

bioavailability

f

t

x

i n s .

BC

is

generally accepted

to b e

r e f r a c t

r

y .

SLIDE 37

R i

Negro

T111

11AZON

T h e R i

N

e g r

is
n

e

f

t h e t h r e e m a j

r

t r i b u t a r i e s

f

t h e A m a z

n

river ( a c c

u

n t i n g f

r

30 %

f

A m a z

n

river discharge).

The

A m a z

n

river

is

t h e l a r g e s t river i n the w

r

l d a c c

u

n t i n g f

r

20 %

f

f r e s h water discharge i n t

t

h e

c

e a n

A TL A N T?C

1

Modhsof 0 C E A N iAmazon

IT

‘ k ’

SLIDE 38 (3

DOM from Rio Negro

2k

451.052 451.092 451.133 451.174

m!z

451.011 451.215 451.256 451.297

C-)

C)

E

I-.

(3 C C

0.1

0.2 0.3 0.4 0.5 0.6 0.7 Atomic 0/C ratio

SLIDE 39

Hydrogen deficient peaks &

possible structures

C

27

H

16

9

OH OH HO

C

26

H

14

9

OH OH HO OH

CO

2 H

CO

2 H

CO

2 H

SLIDE 40

Diluvial humic acid

I-.

Co

C-)

I

C-)

E

4-..

(volcanic ash soil)

J. A. Baldock,
R. J. Smemik,
Org. Geochem.

33, 1093-1109 (2002).

0.5 0.6 0.7

0.1

0.2 0.3 0.4 Atomic 0/C ratio

SLIDE 41 4-’

Cu

C-)

E

BC

i n

rivers

McDonalds Branch DOM

0.1

0.2 0.3 0.4 0.5 0.6 0.7 Atomic

/ C

ratio

Rio Negro DOM

1.6 1.4 1.2 1.0

0.8 0.6 0.4

. 1

0.2 0.3 0.4 0.5 0.6 0.7 Atomic

0/C

ratio

BC

SLIDE 42

IS B C

soluble in

water?

O

x i d a t i

n

i s

an i m p

r

t a n t step for m i c r

b

i a l d e g r a d a t i

n
f

poly-aromatic carbon’.

H O OH

__

H O O C

e.g.)

Q

\

/

M

i c r

b

i a l d e c

m

p

s

i t i

n
f

low rank coal has b e e n r e p

r

t e d . However, it

is

g e n e r a l l y k n

w

n that the d e g r a d a t i

n

p r

c

e s s

i s slow.

1.

A.

Tschech, Forum Mikrobiol.

12, 25 1-264

( 1 9 8 9 ) .

SLIDE 43

I s B C

d e g r a d a b l e ?

.05-0.26 Gt/year

f

BC Global carbon budget Terrestrial: 3,060 Gt

C

Ocean: 40,000 Gt

C

+

Atmosphere: 7 5 G t

C

T

t

a l : 4 3 , 8 1 G t

C 4 3 8 10/0.05

=

8 7 6 , 2 y e a r s 4 3 8 1 / . 2 6

=

1 6 8 , 5

years

A A

*

A

from biomass burning

G

l

d b e r g

Goldberg, B l a c k carbon in the environment (1985) Wiley, New York

SLIDE 44

A

hypothesis

g

l

b

a l

b l a c k carbon

cycle

1 .

BC is a s

u

r c e

f
l

d c a r b

n

in t h e

r i v e r DOM

2.

B C flows i n t

the
c

e a n a n d

is

i n c l u d e d

in

c

e a n i c DOM

3.

B C f l

w

s i n t

the deep
c

e a n

4 .

BC i n

D O M

is

i n c l u d e d into p a r t i c u l a t e

r

g a n i c m a t t e r ( P O M )

5.

B C i n P O M

is

d e p

s

i t e d

to

c

e a n sediment

SLIDE 45

The h y p

t

h e s i s c a n

p a r t l y

s

l

v e

the riddle

in a global

c a r b

n

c y c l e

Selective inclusion

f

refractory component

f

river DOC into

ceanic

D O C pool

“

S i g n i f i c a n t a m

u

n t

f

carbon t r a n s f e r r e d from terrestrial systems to the deep

cean or marine sediments

w

u

l d help b a l a n c e models

f

the global carbon cycle.”

Schlesinger and Melack, Tellus (1981), 33, 172-187

(units: Gt) Adapted from Houghton et. a!.

Climate change

1994 (1995), Cambridge Press,

New York