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

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Molecular Markers and Trace-Metals as Indication of Biomass Combustion in Central Amazon Sediments. Tereza Cristina Oliveira Angela Wagener e Arthur Scofield. [email protected] Objectives and Methods.

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slide1

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

Tereza Cristina Oliveira

Angela Wagener e Arthur Scofield

[email protected]

objectives and methods
Objectives and Methods
  • Characterization of hydrocarbons in sediments of Solimões River and associated lakes prior to oil exploration.
  • Base line and diagnostic origin.
  • Surface sediment sampling in Jun/2005 (wet period) and Nov/2005 (dry period) + cores sediment in 3 lakes.
  • Molecular markers in saturated and aromatic fractions, 38 PAH, trace-metals, ancillary data.
  • GC-MS for organics, ICPMS for metals and TOC for organic carbon.
slide3

6LB

6LA

1LA

1LB

2LB

2LA

Araçá Lake

Preto Lake

Baixio Lake

Study Area

1L Baixio Lake

2L Preto Lake

3S Solimões River

4P Purus River

4S Solimões River

5L Ananá Lake

5S Solimões River

6L Araçá Lake

7L Maracá Lake

7S Solimões Lake

8LP Puraquê Lake

8S Solimões River

8LC Coari Lake

9L Aruã Lake

9U Urucu River

slide5

a

(a)

C29

\

volts

minutes

b

(b)

C30

\

volts

MCNR

minutes

Aliphatic hydrocarbons

  • Chromatograms:
  • Coari-Manaus, 1L
  • 0,82 – 148 mg g‑1
  • (b) Industrial area,
  • IND2
  • 45,6 – 1060 mg g‑1
perylene was the major pah
Perylene was the major PAH

Perylene

70% of ∑PAH

slide7

Parental and Alkylated PAH – Coari-Manaus

Wet

Season

SPAH =

52 – 774ng g-1

Dry

Season

parental and alkylated pah in industrial manaus

90

80

70

60

50

40

30

20

10

0

mg 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

600

500

400

300

200

100

0

mg 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 C3DBT

C1DBT C2DBT C3DBT

Parental and Alkylated PAH in Industrial Manaus

SPAH =

132 - 4713ng g-1

slide9

Wood

Combustion

Motor

Emissions

Mixed

Combustion

Biomass

Combustion

Fl/(Fl + Py)

Petroleum

Combustion

Petroleum

Combustion

C0/(C0 + C1)FlPy

Petroleum

Oil

1.7/(1.7 + 2.6)Dimethylphenanthrene

Diagnostic Ratios

- 1.7/(1.7+2.6)DMPh:

a proxi for combustion

- Fluoranthene/Pyrene

- C0 and C1 homologs

of Fluoranthene and

Pyrene

perylene partly derived from combustion

13 %

66 %

Perylene partly derived from combustion ?
  • Factorial analysis groups " 3-6 rings PAH” (Fl, BaA, BbFl, BaPy, Pe, IPy, Py) and Corg in fator 1 contributing to 66% of the variance.
  • Good correlations of Pe and some trace metals that can be emitted during combustion [Cd (r=0,83), Pb (r=0,77), Cu (r=0,79), Zn (r=0,73)]

Cd → 0,09 – 1,33 mg g-1

Zn → 24,5 – 147 mg g-1

slide11

Early diagenesis of

PAH seen in a core

Confirmed identifying

geochemical precursors

and

slide12

Series of insaturated compounds

and of recent hopanes in 4SII

- hopane

Recent + mature

hopanes in the

industrial area

slide13

3SI

a-Amirina

b-Amirina

Cromatogram of ions for aromatical composite demonstration of natural sources

slide14

Mass spectro

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

conclusions
Conclusions
  • There are no indication of contamination due to ship traffic or oil activities in Coari-Manaus. This is different in industrial Manaus.
  • Early diagenesis at high local temperatures and biological activity interferes with PAH typology.
  • Molecular markers are essential in such cases.
  • In dry periods biomass burning in the “deforestation arc” migrates north and is recorded in sediments.
  • Some of the perylene found in sediments may derive from these events.
  • High fraction of 1.7DMPh in dated core indicate combustion (slash-and-burn) records as early as end 19th century.
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