Carbon isotopic composition in tree-rings:a temperature record and

a tool for biomonitoring CO2 level

Sławomira Pawełczyk and Anna Pazdur

Silesian University of Technology, Institute of Physics, Department of Radioisotopes, Gliwice, Poland,

translocation

stem respiration

ground water

CO213C/12C

temperature

precipitation

assimilationrespiration

glucose13C/12C

starch13C/12C

tree-ring13C/12C

soil water

CO2

cellulose13C/12C

reserves

leaf water

transpiration

latewood13C/12C

earlywood13C/12C

evaporation

Photosynthesis

6CO2+6H 2O+solar energyC6H12O6+6O2

a

i

a

iap c

cb

c

caCC

11313

13Cp – isotopic composition of plant material,13Ca– isotopic composition of the air,a - discrimination against 13C due to diffusion ( 4.4 ‰),b - isotopic discrimination during carboxylation ( 27 ‰),ci - internal CO2 concentration,ca - atmospheric CO2 concentration CO2

stomata

water

sample collection site

BALTIC SEA

POLAND

Augustów

Cracow

Warsaw

LITHUANIA

BELARUS

UKRAINE

ChorzówRuda Śląska

Map of Poland with location of sample collection sites

Mass spectrometerMI - 1305

Liquid scintillation betaspectrometer

QUANTULUS 1220

extraction in Soxhlet’s apparatus

separation of latewood

benzene

-cellulose

14C13C

WOOD(cross-section of trunk)

separation of tree-rings represent successive growth years

carbon dioxide

a)

1860 1880 1900 1920 1940 1960-100

-50

0

50

100

150

200

250

300

350

400

450

500

Year

14 C

[‰

]

Augustów

1960 1965 1970 1975 1980 1985 1990 1995 2000 2005-100

0

100

200

300

400

500

600

700

800

Year

14 C

[‰

]

b)

ChorzówRuda ŚląskaCracowSchauinsland

Annual changes of 14C in tree rings from Augustów (part a),Ruda Śląska, Chorzów and Cracow (part b)

C h a n g e s o f c o m p o n e n t v a l u e C f o s s i l f o r R u d a Ś l ą s k a , C h o r z ó w a n d C r a c o w

0

5

1 0

1 5

2 0

2 5

3 0

3 5

1 9 6 5 1 9 7 5 1 9 8 5 1 9 9 5

R u d a Ś l ą s k a

C h o r z ó w

C r a c o w

,%100

14

1414

backgr

backgrbackgrfossil

C

CCCC

w h e r e :

C b a c k g r , 1 4 C b a c k g r – C O 2 ( p p m v ) a n d 1 4 C ( p M C ) c o n c e n t r a t i o n i n t h e “ c l e a n a i r ” , S c h a u i n s l a n d

( L e v i n e t . a l . , 1 9 9 5 , L e v i n a n d K r o m e r , 1 9 9 7 ) ,

1 4 C – r a d i o c a r b o n c o n c e n t r a t i o n f o r t h e e x a m i n e d r e g i o n i n ( p M C ) .

Y e a r

Cfo

ssil

[ppm

v]

Warsaw (52°12’N, 21°10’E)Kaunas(54º88’N, 23º88’E)Vilnius (54º63’N, 25º28’E)Cracow (50°03’N, 19°03’E)

Augustów (53°51’N, 22°58’E)

PinePinus sylvestris

Shape of a pine crown

Needles, seedling,seed,cone

Cross - section fragment of trunk

Annual average temperature(according to IMGW)

Meteorological data:

Diposition of temperature in Europe

Augustów

Kowno

Wilno

1414

1860 1880 1900 1920 1940 19600

20

40

60

80

100

120

140

160

Year

Suns

pot N

umbe

rs

0

20

40

60

80

100

120

140

160A

a indices

oo

o1213

121313

1312141214

ooo

1214

121414

10001/

/

1000252

1//

10001/

/

PDB

norm

NBS

norm

CCCC

CCCCC

CC

CCC

Fig.1. Observed sunspot numbers and Aa indices

Fig.2. 14C in the 1861-954 tree-rings of pine from Augustów Wilderness, Poland

Sunspot numbersAa indices

1860 1880 1900 1920 1940 1960-100

-80

-60

-40

-20

0

20

40

Year

Δ14

C [

‰]

1860 1880 1900 1920 1940 1960-100

-80

-60

-40

-20

0

20

40

Year

14C

[‰

]

This work

Stuiver et al. (1998)

Fig.3. 14C in the 1861-954 tree-rings of pine from Augustów Wilderness. For comparison, the measurements by Stuiver et al. are also ploted

1950 1952 1954 1956 1958 1960 1962 1964 -100

0

100

200

300

400

500

600

700

Year

14 C

[‰

]

C in tree rin g s o f tre e sp ec ie s fro m d iffe ren t s ite s :14

P in e (P in u s sy lv estris ) , A u g u stó w (5 3 5 1 'N , 2 2 5 8 'E ),

, M a ck e n z ie (6 8 N , 1 3 0 W ), K a iM ei i F an cy (1 9 8 6 ),

, C h in a (4 7 N , 1 2 9 E ), K a iM ei i F an cy (1 9 8 6 ),

, Yu n n a n (2 7 N , 1 0 0 E ) K a iM e i i F an c y (1 9 8 6 ),

(L ag aro stro b o s fran k lin ii) , Tasm an ia (4 1 S , 1 4 5 E ) H u a (2 0 0 0 ),

(P in u s k es iy a ), T h a ilan d (1 8 N , 9 8 E ) H u a (2 0 0 0 ).

o o

o o

o o

o o

o o

o o

S p ru ce

S p ru ce

S p ru ce

P in e

P in e

e t a l.

e t a l.

1860 1880 1900 1920 1940 1960 -100

-80

-60

-40

-20

0

20

40

Year

14

C [

‰]

0

20

40

60

80

100

120

140

160

Num

ber of sun spots

14C number of sun spots

Years 1861-1955 n = 95 r = -0 .03Years 1861-1930 n = 70 r = +0.15

Years 1858-1927 n = 70 r = -0.26

3 yea rs sh ift in C (tim e o f carbon exchange betw een stra tosphere and troposphere )

14

C o m p ariso n o f C in tree r in g s fro m A u g u s tó w w ith su n sp o ts n u m b er.

P inus sy lvestris14

Fig. 4. 14C in 1861 – 1898 tree-rings from Augustów Wilderness and sunspot numbers. The correlation coefficient, with 14C values delayed by 4 years is – 0.41 (n = 37, p < 0.02 )

Fig.5. 14C in 1861 – 1898 tree-rings from Augustów Wilderness and Aa indices. The correlation coefficient, with 14C values delayed by 4 years is – 0.27 (n = 37, p < 0.1)

1860 1865 1870 1875 1880 1885 1890 1895 1900-50

-40

-30

-20

-10

0

10

20

Year

D14

C

14Csunspot number

1860 1865 1870 1875 1880 1885 1890 1895 1900 -50

-40

-30

-20

-10

0

10

20

Year

14 C

[‰

]

5

10

15

20

25

Aa indices

14CAa indices

S p ec tru m a n a ly s is o f C in th e p e r io d 1 8 6 1 -1 9 5 5 . 14

0 0,1 0,2 0,3 0,4 0,5 0

10

20

30

40

50

60

70

Frequency [1/year]

Den

sity

of

pow

er s

pect

rum

31,3

8,5

1860 1880 1900 1920 1940 1960 -100

-80

-60

-40

-20

0

20

40

Year

14 C

[‰

]

0

-1

1

2

3

4

5

6 x 10

7

CO

2 emission [carbon tons /year]

a 14C CO2 emission

14C in wood as a tool for biomonitoring CO2 level

0 1 2 3 4 5 6

x 10 7

-100

-80

-60

-40

-20

0

20

40

CO2 emission [carbon tons/year]

14 C

[‰

]

14C = -410-7 e– 0,691 r = -0,23, n = 95, p<0,01

b

14C [‰] = a·e + b

relationship for years 1861 – 1955

Years

CH2

2 2 C

OHCuO

2. Latewood

Na ClO2

CH3COOH

holocellulose

NaOH

- cellulose

Cross - section fragment of pine trunk

1. Resin extraction in Soxhlet’s apparatus

The Soxhlet thimble usedin the extraction of - cellulose

3.

O HO O HO + CO Mass spectrometer OH n 450 18 h

- cellulose

Preparation of - cellulose and 13C measurements

Accuracy of measurement:0.05‰

ooo

1213

121313 10001

//

PDBCCCC

C

No 170 mm

20 mm

latewood

earlywood

tree-ring

1890 1900 1910 1920 1930 1940 1950 1960 1970 -26,5

-26

-25,5

-25

-24,5

-24

-23,5

-23

-22,5

Yearr

13 C

[‰

]

16

17

18

19

20

21

22 Average tem

perature VII – V

III [ C]

13C in -cellulose for latewood average temperatureVII - VIII

a

16 17 18 19 20 21 22 -26,5

-26

-25,5

-25

-24,5

-24

-23,5

-23

-22,5

Average temperature VII – VIII [ºC]

13 C

[‰

]

13C = 0,36 t– 31,40 r = 0,49, n = 70, p<0,001

b

16 17 18 19 20 21 22 -26

-25.5

-25

-24.5

-24

-23.5

-23

-22.5

Average temperature VII – VIII [ºC]

13 C

[‰

]

13C = 0,51 t - 34,01 r = 0,71, n =50, p<0,001

relationship for years 1899 –1948

relationship for years 1899 –1968

1890 1900 1910 1920 1930 1940 1950 1960 1970 14

15

16

17

18

19

20

21

22

Year

Ave

rage

tem

pera

ture

VII

, VII

I [

C]

Warsaw Kaunas Vilnius Cracow

d

0

0,1

0,2

0,3

0,4

0,5

V VI VII VIII IX

Month

r

-0,2

-0,1

0

0,1

0,2

0,3

VIII a IX a X a XI a XII a I a II a III a IV a V VI VII VIII

Month

r

1890 1900 1910 1920 1930 1940 1950 1960 1970 -29

-28

-27

-26

-25

-24

-23

-22

Year

13 C

[‰

]

13C in -cellulose for latewood 13C in wholewood

a 13C in tree-rings as a temperature record

b

c

Correlation coefficient between 13C values for wholewood and average temperatures

Correlation coefficient between 13C in -cellulose from latewoodand average temperatures

13C in wholewood as a tool for biomonitoring CO2 level

13C in wholewood CO2 emission estimated by Marland at al. (2001)

1860 1880 1900 1920 1940 1960 1980 -29

-28

-27

-26

-25

-24

-23

Year

13 C

[‰

]

0

1

2

3

4

5

6

7

8 x 10 7

CO

2 emission [carbon tons/year]

a

0 1 2 3 4 5 6 7 8 x 10 7

-29

-28

-27

-26

-25

-24

-23

CO2 emission [carbon ton/year]

13 C

[‰

]

13C = -910-9 e – 25,724 r = -0,2, n = 108, p<0,02

b

0 1 2 3 4 5 6 7 8

x 10 7

-29

-28

-27

-26

-25

-24

-23

CO2 emission[carbon tons/year]

13 C

[‰

]

13C = -2·10-8e – 25,116 r = -0,54, n = 79, p<0,001 relationship for years 1861 - 1968

relationship for years 1890 - 1968

13C = a·e + b

Years

13C in late wood as a tool for biomonitoring CO2 level

13C in -cellulose from latewood CO2 emission

1890 1900 1910 1920 1930 1940 1950 1960 1970 -26,5

-26

-25.5

-25

-24,5

-24

-23,5

-23

-22,5

Year

13 C

[‰

]

7

0

1

2

3

4

5

6

7

8 x 10

CO

2 emission [carbon tons/year]

a

0 1 2 3 4 5 6 7 8

x 10 7

-26,5

-26

-25,5

-25

-24,5

-24

-23,5

-23

-22,5

CO2 emission [carbon tons/year]

13 C

[‰

]

13C = -710-9 e – 24,685 r = -0,15, n = 70, p<0,3

b

0 1 2 3 4 5 6

x 10 7

-26,5

-26

-25,5

-25

-24,5

-24

-23,5

-23

-22,5

CO2 emission[carbon tons /year]

13 C

[‰

]

13C = -210-8 e – 24,357 r = -0,36, n = 64, p<0,005 relationship for years 1899 -1968

relationship for years 1899 -1962

13C = a·e + b

Years

,,,,13 eptyfC

y

y

y

ye

e

C

y

yp

p

C

y

yt

t

C

y

eptyC

13131313 ,,,,

present climate (temperature and precipitation)

13C of air atmospheric trend

universal and local effect

13C tree ring

temporary and local effect

climate of past years

the tree’s ecosystem

potential for growth”

13C in -cellulose from latewoodand CO2 concentration in atmosphere

partial derivative of13C towards time (in years)

partial derivative of13C towards temperature

partial derivative of13C towards precipitation

partial derivative of13C towards CO2 emissionn

changes of temperature in time

changes of CO2 in time

changes of 13C under the influence of additional factors, for example: „potential for growth”,carbon flux from biosphere do atmosphere or error connected with establishment

changes of precipitation in time

, ,

yty C‰/º51,01

ypy mm-0,00217‰/2

yecarbon) of ‰/(ton102y3 8

RyyyyC 32113

Assuming:

the following relation is valid:

1890 1900 1910 1920 1930 1940 1950 1960 1970 -26,5

-26

-25,5

-25

-24,5

-24

-23,5

-23

-22,5

Year

13 C

[‰

]

13C 1 2 3

1890 1900 1910 1920 1930 1940 1950 1960 1970 -2

-1

0

1

2

3

Year

Fluctuation of measured 13C Fluctuation of determined 13C (1+2+3)

a

1890 1900 1910 1920 1930 1940 1950 1960 1970 -1.5

-1

-0.5

0

0.5

1

1.5

2

Year

Fluctuation of measured 13C Fluctuation of determined 13C (1+2)

b

1890 1900 1910 1920 1930 1940 1950 1960 1970 -1,5

-1

-0,5

0

0,5

1

1,5 x 10

8

Year

CO

2 em

issi

on

CO2 emission estimated on the basis of measured 13C

CO2 emission estimated by Marland et al. (2001)

Comparison between trends

1890 1900 1910 1920 1930 1940 1950 1960 1970 -1.5

-1

-0.5

0

0.5

1

1.5 x 10

8

Year

CO

2 em

issi

on

CO2 emission estimated on the basis of measured 13C

CO2 emission estimated by Marland et al. (2001)

c

THE END

Thank you for attention