Molecular Markers and Trace-Metals as Molecular Markers and Trace-Metals as Indication of Biomass Combustion in Indication of Biomass Combustion in

Central Amazon SedimentsCentral Amazon Sediments

Tereza Cristina OliveiraTereza Cristina OliveiraAngela Wagener e Arthur ScofieldAngela Wagener e Arthur Scofield

tereza.cristina@piatam.org.brtereza.cristina@piatam.org.br

Objectives and MethodsObjectives and Methods

Characterization of hydrocarbons in sediments of Characterization of hydrocarbons in sediments of SolimSolimões River ões River and associated lakes and associated lakes prior to oil prior to oil exploration.exploration.

Base line and diagnostic origin.Base line and diagnostic origin. Surface sediment sampling in Jun/2005 (wet Surface sediment sampling in Jun/2005 (wet

period) and Nov/2005 (dry period) + cores period) and Nov/2005 (dry period) + cores sediment in 3 lakes.sediment in 3 lakes.

Molecular markers in saturated and aromatic Molecular markers in saturated and aromatic fractions, 38 PAH, trace-metals, ancillary data.fractions, 38 PAH, trace-metals, ancillary data.

GC-MS for organics, ICPMS for metals and TOC for GC-MS for organics, ICPMS for metals and TOC for organic carbon.organic carbon.

Study Area

1LB1LA

Baixio Lake

2LB

2LA

Preto Lake

6LB6LA

Araçá Lake

1L Baixio Lake2L Preto Lake3S Solimões River4P Purus River4S Solimões River5L Ananá Lake5S Solimões River6L Araçá Lake7L Maracá Lake7S Solimões Lake8LP Puraquê Lake8S Solimões River8LC Coari Lake9L Aruã Lake9U Urucu River

Sampling

Chromatograms:

(a)Coari-Manaus, 1L0,82 – 148 g g‑1

(b) Industrial area, IND245,6 – 1060 g g‑1

C29

\

(a)

volt

s

minutes

aa

(b)

volt

s

minutes

MCNR

C30

\

bb

Aliphatic Aliphatic hydrocarbonshydrocarbons

PerilenoPerileno

RT: 0.00 - 59.49

0 5 10 15 20 25 30 35 40 45 50 55Time (min)

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bun

dan

ce

44.19

39.54

36.75 45.0747.64

31.2450.78 54.81

14.9018.50

21.7311.08 24.51

NL:5.85E6TIC F: MS PT6LA C1B F201

Perylene was the major PAHPerylene was the major PAH

70% of ∑PAH

Perylene

0

4

8

12

16

20N

C1N

C2N

C3N

C4N

AC

EF

AC

E FC

1FC

2FC

3F Ph

C1P

hC

2Ph

C3P

hC

4Ph A Fl

Py

C1P

yC

2Py

B(a

)A Ch

C1C

hC

2Ch

B(b

)Fl

B(k

)Fl

B(a

)Py

Ipy

DB

(ah

)AB

(gh

i)P

ER

DB

TC

1DB

TC

2DB

TC

3DB

T

ug

/kg

2L

4S

8LP

0

5

10

15

20

25

30

NC

1N

C2

NC

3N

C4

NA

CE

FA

CE F

C1

FC

2F

C3

FP

hC

1P

hC

2P

hC

3P

hC

4P

h A Fl

Py

C1

Py

C2

Py

B(a

)A Ch

C1

Ch

C2

Ch

B(b

)Fl

B(k

)Fl

B(a

)Py

Ipy

DB

(ah

)AB

(gh

i)P

ER

DB

TC

1D

BT

C2

DB

TC

3D

BT

ug

/kg

2L

4S

8S

WetWetSeasonSeason

DryDrySeasonSeason

Parental and Alkylated PAH – Coari-ManausParental and Alkylated PAH – Coari-Manaus

PAH =

52 – 774 ng g-1

Parental and Alkylated PAH in Parental and Alkylated PAH in Industrial ManausIndustrial Manaus

0

100

200

300

400

500

600

N C1N C2N C3N C4N F C1F C2F C3F Fen C1Fen C2Fen C3Fen C4Fen Pi C1Pi C2Pi CRIS C1CRIS C2CRIS DBT C1DBT C2DBT C3DBT

(ng

g-1

)

IND1

IND2

IND3

IND4

IND5

(b)

(g

kg-1)

N C1N C2N C3N C4N F C1F C2F C3F Ph C1Ph C2Ph C3Ph C4Ph Py C1Py C2Py Ch C1Ch C2Ch DBT C1DBT C2DBT C2DBT

0

100

200

300

400

500

600

N C1N C2N C3N C4N F C1F C2F C3F Fen C1Fen C2Fen C3Fen C4Fen Pi C1Pi C2Pi CRIS C1CRIS C2CRIS DBT C1DBT C2DBT C3DBT

(ng

g-1

)

IND1

IND2

IND3

IND4

IND5

(b)

0

100

200

300

400

500

600

N C1N C2N C3N C4N F C1F C2F C3F Fen C1Fen C2Fen C3Fen C4Fen Pi C1Pi C2Pi CRIS C1CRIS C2CRIS DBT C1DBT C2DBT C3DBT

(ng

g-1

)

IND1

IND2

IND3

IND4

IND5

(b)

(g

kg-1)

N C1N C2N C3N C4N F C1F C2F C3F Ph C1Ph C2Ph C3Ph C4Ph Py C1Py C2Py Ch C1Ch C2Ch DBT C1DBT C2DBT C2DBTC1DBT C2DBT C3DBT

600

500

400

300

200

100

0

g k

g-1

N C1N C2N C3N C4N F C1F C2F C3F Ph C1Ph C2Ph C3Ph C4Ph Py C1Py C2Py Ch C1Ch C2Ch DBT C1DBT C2DBT C3DBT

90

80

70

60

50

40

30

20

10

0 0

10

20

30

40

50

60

70

80

90

N Aceft Ace F Fen A Fl Pi BaA CRIS BbFl BkFl BaPi Ipi DahA BghiPe

IND1

IND2

IND3

IND4

IND5

(a)

N ACEF ACE F Ph A Fl Py B(a)A Ch B(a)Fl B(k)Fl B(a)Py Ipy DB(ah)A B(ghi)PER

(g

kg-1

)

0

10

20

30

40

50

60

70

80

90

N Aceft Ace F Fen A Fl Pi BaA CRIS BbFl BkFl BaPi Ipi DahA BghiPe

IND1

IND2

IND3

IND4

IND5

(a)

0

10

20

30

40

50

60

70

80

90

N Aceft Ace F Fen A Fl Pi BaA CRIS BbFl BkFl BaPi Ipi DahA BghiPe

IND1

IND2

IND3

IND4

IND5

(a)

N ACEF ACE F Ph A Fl Py B(a)A Ch B(a)Fl B(k)Fl B(a)Py Ipy DB(ah)A B(ghi)PER

(g

kg-1

)g

kg

-1

N ACEF ACE F Ph A Fl Py B(a)A Ch B(a)F B(k)Fl B(a)Py Ipy DB(ah)A B(ghi)PER

PAH = 132 - 4713 ng g-1

- - 1.7/(1.7+2.6)DMPh: 1.7/(1.7+2.6)DMPh: a proxi for a proxi for combustioncombustion

- - Fluoranthene/PyreneFluoranthene/Pyrene

- - CC00 and C and C11 homologs homologs of Fluoranthene andof Fluoranthene and PyrenePyrene

MotorEmissions

MixedCombustion

WoodCombustion

BiomassCombustion

PetroleumCombustion

Petroleum

Combustion

Petroleum

Fl/(

Fl +

Py)

C0/(

C0 +

C1)F

lPy

1.7/(1.7 + 2.6)Dimethylphenanthrene

Oil

Diagnostic RatiosDiagnostic Ratios

Perylene partly derived from Perylene partly derived from combustion ?combustion ?

Factorial analysis Factorial analysis groups groups "" 3-6 rings PAH” 3-6 rings PAH” (Fl, BaA, BbFl, BaPy, Pe, (Fl, BaA, BbFl, BaPy, Pe, IPy, Py) and Corg in IPy, Py) and Corg in fator 1 contributing to fator 1 contributing to 66% of the variance.66% of the variance.

Good correlations of Pe Good correlations of Pe and some trace metals and some trace metals that can be emitted that can be emitted during combustion [Cd during combustion [Cd (r=0,83), Pb (r=0,77), (r=0,83), Pb (r=0,77), Cu (r=0,79), Zn Cu (r=0,79), Zn (r=0,73)](r=0,73)]

13

%1

3 %

66 %66 %

Cd → 0,09 – 1,33 g g-1

Zn → 24,5 – 147 g g-1

Early diagenesis Early diagenesis ofofPAH seen in a PAH seen in a corecore

Confirmed Confirmed identifyingidentifyinggeochemical geochemical precursorsprecursorsandand

6LB Naphthalenes

0

2

4

6

8

10

(g

kg

-1) N

C1N

C2N

C3N

C4N

Fluorenes

0

5

10

15

20

25

30

35(

g k

g-1

) F

C1F

C2F

C3F

Phenanthrenes

0

5

10

15

20

25

5 10 20 30 40 50

Depth (cm)

(g

kg

-1)

Ph

C1Ph

C2Ph

C3Ph

C4Ph

6LB Pyrenes

0

10

20

30

40

50

60

(g

kg

-1)

Py

C1Py

C2Py

Chrysenes

0.0

1.0

2.0

3.0

4.0

(g

kg

-1)

Ch

C1Ch

C2Ch

Dibenzothiophenes

0

5

10

15

20

25

5 10 20 30 40 50Depth (cm)

(g

kg

-1)

DBT

C1DBT

C2DBT

C3DBT

R T : 2 0 . 0 0 - 5 5 . 0 0

2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5T i m e ( m i n )

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

la

ti

ve

A

bu

nd

an

ce

3 9 . 1 13 7 . 9 0

3 6 . 2 14 0 . 7 3

2 8 . 3 7

3 5 . 6 9 4 0 . 9 22 9 . 1 0 4 2 . 1 53 1 . 7 6

4 2 . 4 83 4 . 8 92 5 . 7 5 4 4 . 0 82 4 . 4 3 4 4 . 5 5 4 6 . 3 7 4 8 . 9 62 4 . 2 6 5 1 . 8 1

N L :1 . 6 1 E 6m / z = 1 9 0 . 5 0 -1 9 1 . 5 0 F : M S IN D 2 _ n o v 04 _ 0 1

H30H29

TC24

Tm

TsTC26

H31(R/S)

H31-H35(R/S)-hopanos

H32(R/S)H33(R/S)H34(R/S)

H35(R/S)

IND2

R T : 2 0 . 0 0 - 5 5 . 0 0

2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5T i m e ( m i n )

0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

8 0

9 0

1 0 0

Re

la

ti

ve

A

bu

nd

an

ce

3 9 . 1 13 7 . 9 0

3 6 . 2 14 0 . 7 3

2 8 . 3 7

3 5 . 6 9 4 0 . 9 22 9 . 1 0 4 2 . 1 53 1 . 7 6

4 2 . 4 83 4 . 8 92 5 . 7 5 4 4 . 0 82 4 . 4 3 4 4 . 5 5 4 6 . 3 7 4 8 . 9 62 4 . 2 6 5 1 . 8 1

N L :1 . 6 1 E 6m / z = 1 9 0 . 5 0 -1 9 1 . 5 0 F : M S IN D 2 _ n o v 04 _ 0 1

H30H29

TC24

Tm

TsTC26

H31(R/S)

H31-H35(R/S)-hopanos

H32(R/S)H33(R/S)H34(R/S)

H35(R/S)

IND2

Series of insaturated compounds and of recent hopanes in 4SII

Recent + mature hopanes in the industrial area

- hopane

Cromatogram of ions for aromatical composite demonstration of natural sources

RT: 9.79 - 55.03

10 15 20 25 30 35 40 45 50 55Time (min)

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

39.42

26.9134.11

36.51

30.19 47.1044.7749.02

49.7323.8614.39

21.98 50.8817.8810.80

NL:1.96E6TIC F: MS PT03 S F201

3SI

E

D

E

D

E

D

E

D

EE

E

E

DC

BB

C D

E

HOHO

AHO

C

B

D

- Amerina - AmerinaLupeol

E

-Amirina -Amirina

Mass spectroPT03 S F202 #4021 RT: 42,48 AV: 1 SB: 1 42,57 NL: 5,66E4T: + c Full ms [ 55,00-450,00]

100 150 200 250 300 350 400 450

m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Re

lative

Ab

un

da

nce

145,3

144,3

157,2172,2

143,3

129,2378,181,3 95,3 173,2 232,2195,2 379,2240,2 267,1 396,2377,1293,1 352,2 425,1

m/z 378

(Wolf et al., 1989; Bouloubassi & Saliot, 1993; Abas et al. 1995, Buldizinsk et al. 1997 Somoneit, 2005; e Simoneit, 2005;).

ConclusionsConclusions

There are no indication of contamination due to There are no indication of contamination due to ship traffic or oil activities in Coari-Manaus. This is ship traffic or oil activities in Coari-Manaus. This is different in industrial Manaus.different in industrial Manaus.

Early diagenesis at high local temperatures and Early diagenesis at high local temperatures and biological activity interferes with PAH typology.biological activity interferes with PAH typology.

Molecular markers are essential in such cases.Molecular markers are essential in such cases. In dry periods biomass burning in the In dry periods biomass burning in the

“deforestation arc“deforestation arc” migrates north and ” migrates north and is is recorded in sediments.recorded in sediments.

Some of the perylene found in sediments may Some of the perylene found in sediments may derive from these events.derive from these events.

High fraction of 1.7DMPh in dated core indicate High fraction of 1.7DMPh in dated core indicate combustion (combustion (slash-and-burnslash-and-burn) records as early as ) records as early as end 19end 19thth century. century.

Obrigada!