GeolCarp_Vol63_No5_399

www.geologicacarpathica.sk

GEOLOGICA CARPATHICA

, OCTOBER 2012, 63, 5, 399—405 doi: 10.2478/v10096-012-0031-5

New geochemical data on fossil wood from the Albian of the

Dolomites (Southern Alps, Italy)

ALEXANDER LUKENEDER

, ACHIM BECHTEL

and REINHARD GRATZER

Natural History Museum, Geological-Paleontological Department, Burgring 7, 1010 Wien, Austria; alexander.lukeneder@nhm-wien.ac.at

Department of Applied Geosciences and Geophysics, University of Leoben, Peter-Tunner-Str. 5, A-8700 Leoben, Austria;

achim.bechtel@unileoben.ac.at; reinhard.gratzer@unileoben.ac.at

(Manuscript received November 15, 2011; accepted in revised form March 13, 2012)

Abstract: Information is provided about organic-matter bearing sediments and fossil drift-wood from the Puez area
(Col de Puez, Southern Alps) near Wolkenstein (S. Tyrol, Italy). The locality is located on the Trento Plateau which
represents a submarine high during the Lower Cretaceous. Its terpenoid hydrocarbon composition indicates that the
wood fragment derived from a conifer belonging to the family Podocarpaceae or Araucariaceae. Intense degradation of
OM argues for lengthier drifting. Long-term drifting is also indicated by the infestation of the bivalve Teredo (“ship-
worm”). The finding of a fossil tree trunk sheds some light on the early Lower Cretaceous tectonic history of the Trento
Plateau and the Dolomites.

Key words: Drift-wood, Albian, Early Cretaceous, Dolomites, Italy.

Introduction

The geology of the Dolomites and adjacent areas has recent-
ly  been  summarized  in  detail  by  Lukeneder  &  Aspmair
(2006), and Lukeneder (2008, 2010, 2011). According to re-
cent investigations by Muttoni et al. (2005), the Lombardian
Basin – and thus the adjacent Trento Plateau to the east –
were  located  at  approximately  35 °N  to  25 °N  in  the  Early
Jurassic,  at  10 °N  in  the  Middle—Late  Jurassic  (lowest  lati-
tude  in  the  Kimmeridgian),  at  approximately  20 °N  in  the
Valanginian-Hauterivian  time  and  back  to  almost  30 °N  in
the Early Cretaceous (Aptian).

The complex Mediterranean paleogeography of Jurassic

and  Cretaceous  domains  (Fourcade  et  al.  1993)  is  character-
ized  by  microplates  within  the  Tethyan  oceanic  corridor  be-
tween  the  African  and  European  landmasses  (Dercourt  et  al.
1993;  Cecca  1998;  Zharkov  et  al.  1998;  Stampfli  &  Mosar
1999; Scotese 2001; Stampfli et al. 2002). The region of the
Southern Alps, including the investigated area (i.e. Puez area),
was  situated  on  the  northern  border  to  the  Penninic  Ocean
( = Alpine  Tethys)  during  the  Jurassic  and  Early  Cretaceous.
This  area  represents  a  passive  continental  margin  of  the
Apulian  Plate  (Jud  1994)  of  the  South  Alpine-Apennine
Block. It was delimited by the Penninic Ocean to the north-west
and the Vardar Ocean to the south-east (Dercourt et al. 1993;
Stampfli & Mosar 1999; Scotese 2001; Stampfli et al. 2002).

The stratigraphy of the Lower Cretaceous sediments here is

based on micro- and nannofossils (e.g. foraminifera, calpio-
nellids and dinoflagellates; see also Lukeneder 2010) and
macrofossils (ammonites; Lukeneder 2012).

The main goal is to present new geochemical data on Lower

Cretaceous fossil wood from the Dolomites. The presented
data provide the first insights into Albian fossil wood from the
Dolomites and were collected within the Dolomite Project
P20018-N10 (Project of the Austrian Science Fund FWF).

Geographical and geological setting

Geography

The outcrop is situated on the Puez-Odle-Gardenaccia Pla-

teau  in  the  Dolomites,  30 km  northeast  of  Bozen,  6 km
northeast of Wolkenstein ( = Selva in Val. Gardena,  = Sölva),
in the Department Trentino-Alte Adige (maps Trentino – Alto
Adige;  South  Tyrol,  Italy;  Tappeiner  2003).  The  locality  is
situated in the heart of the natural park Puez-Odle within the
UNESCO  world  heritage  area  of  the  Dolomites  (Lukeneder
2010, 2011, 2012; Fig. 1).

Geological setting

The Puez area is situated on the northernmost part of the

Trento  Plateau  within  the  Dolomites,  formed  on  a  Creta-
ceous submarine plateau, the Puez-Gardenaccia Plateau. The
Dolomites (Permian to Cretaceous) are an internal part of the
Southern  Alps,  representing  a  Northern  Italian  mountain
chain  that  emerged  during  the  deformation  of  the  passive
continental margin of the Adriatic (Jud 1994; Bosellini et al.
2003; Castellarin et al. 2006). For a more detailed geology of
the Puez area see Lukeneder (2010, 2011, 2012).

The Albian Puez-Marl Member (approximately 60 m, Early

Albian—Early  Cenomanian)  encompasses  the  marl-rich  upper
part of the Puez Formation (for a discussion see Lukeneder &
Aspmair  2006;  Lukeneder  2008,  2010,  2012).  The  analysed
tree  trunk  derives  from  the  mid  part  of  this  member,  section
Puez/P2 (bed P2/160; Figs. 1—2).

Biostratigraphical data (Lukeneder 2010; pers. comm. J.

Soták) indicate Hedbergella ssp. and Rotalipora ssp. (up to
the Thalmanninella globotruncanoides Biozone) along with
calcareous nannofossils such as Eiffellithus ssp. (up to latest
Albian CC9 Zone) and hint at an Early Albian to Late Albian

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LUKENEDER, BECHTEL and GRATZER

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GEOLOGICA CARPATHICA, 2012, 63, 5, 399—405

age (perhaps up to the Albian/Cenomanian boundary) for the
Puez-Marl Member. The drift wood bed P2/160 shows Mid
Albian age.

Material and methods

Drifted wood is not known from the Lower Cretaceous of

the  Southern  Alpine  region  so  far.  The  tree  trunk  (approxi-
mately 15 20 cm) derives from the mid part of the section
Puez/P2  (log P2/160;  Figs. 1—2).  The  specimen  is  covered
by a yellowish layer consisting of limonite (Fig. 2). The still
attached  surrounding  sediment  comprised  radiolarians  and
foraminifera. The trunk is well preserved and each wood fi-
bre and cell is visible in detail. The specimen shows a trunk
with the branching of a limb.

Beds were sampled for biostratigraphical (macro- and mi-

crofossils), and geochemical (CaCO

) data. Calcium carbon-

ate contents (CaCO

; wt. % bulk rock, total carbonate) were

determined using the carbonate bomb technique. All the
chemical analyses were carried out in the laboratories of the
Department of Applied Geosciences and Geophysics, Mon-

tanuniversität Leoben. Samples are stored at the Natural His-
tory Museum of Vienna (NHMW), in the collection of the
Department of Geology and Palaeontology with inventory
number from NHMW 2010/0095/0001. Microfossil analysis
includes preliminary studies of forminifera by Ján Soták.

Organical geochemistry

For organic geochemical analyses, representative portions

of selected samples were extracted for approximately 1 h us-
ing  dichloromethane  in  a  Dionex  ASE  200  accelerated  sol-
vent extractor at 75 °C and 50 bar. After evaporation of the
solvent  to  0.5 ml  total  solution  in  a  Zymark  TurboVap  500
closed cell concentrator, asphaltenes were precipitated from
a hexane-dichloromethane solution (80 : 1) and separated by
centrifugation.  The  fractions  of  the  hexane-soluble  organic
matter  were  separated  into  NSO  compounds,  saturated  hy-
drocarbons, and aromatic hydrocarbons by medium-pressure
liquid  chromatography  using  a  Köhnen-Willsch  MPLC  in-
strument (Radke et al. 1980).

The saturated and aromatic hydrocarbon fractions were

analysed on a gas chromatograph equipped with a 30-m DB-1

Fig. 1. Locality map of the Puez area with indicated outcrop position of the main log Puez P2 within the Dolomites (S. Tyrol, Italy). A – Puez
area (white star) and indicated outcrop position (P1). B – Detailed position of the drift-wood bed P2 160 at the Col de Puez section.
B1 – Enlarged part of the dark, marl-bed P2 160. C – Position of the Puez Locality on the Trento Plateau. D – East-west transect during the
Lower Cretaceous plateau-basinal sequence of the South Alpine region, (not palinspastically corrected), modified after Caracuel et al. (1997)
and Préat et al. (2006). Note indicated drift wood. Adapted after Lukeneder (2011, 2012).

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NEW GEOCHEMICAL DATA ON FOSSIL WOOD FROM THE ALBIAN OF THE DOLOMITES (ITALY)

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GEOLOGICA CARPATHICA, 2012, 63, 5, 399—405

Fig. 2. Lithostratigraphic column with plotted carbonate content around the drift-wood bed P2/160. Note the indicated grey-bold line which
marks the position of bed P2/160, the drift-wood bed. A – Frontal view of the drift wood showing limonitic preservation on surface. B – Top
view of the same specimen.

fused silica capillary column (i.d. 0.25 mm; 0.25-mm film
thickness) and coupled to a Finnigan MAT GCQ ion trap mass
spectrometer. The oven temperature was programmed from
70° to 300 °C at a rate of 4 °C · min

—1

followed by an isother-

mal  period  of  15 min.  Helium  was  used  as  carrier  gas.  The
sample was injected splitless with the injector temperature at
275 °C. The mass spectrometer was operated in the EI (elec-
tron impact) mode over a scan range from m/z 50 to m/z 650
(0.7 s  total  scan  time).  Data  were  processed  with  a  Finnigan
data  system.  Individual  compounds  were  identified  based  on
retention time in the total ion current (TIC) chromatogram and
then comparing the mass spectra with published data. Relative
percentages and absolute concentrations of different compound
groups  in  the  saturated  and  aromatic  hydrocarbon  fractions
were calculated using peak areas from the gas chromatograms
in  relation  to  those  of  internal  standards  (deuterated  n-tetra-
cosane  and  1.1

’-binaphthyl, respectively). The concentrations

were normalized to the total organic carbon content.

Results and discussion

Molecular composition of hydrocarbons

n-Alkanes, isoprenoids

predominance, as indicated by values of the Carbon Prefer-
ence Index (CPI) between 1.2 and 1.4 (Table 2; Fig. 3). The
CPI was calculated from the concentrations of individual n-al-
kanes using the formula of Bray & Evans (1961). Long-chain
(C

—C

) n-alkanes are interpreted to be derived from vascu-

lar plants, where they occur as the main components of plant
waxes (Eglinton & Hamilton 1967). Clearly, land plant or-
ganic matter had experienced aerobic degradation before its
deposition in the sedimentary environment.

The fossil wood sample is characterized by the complete

absence of short-chain n-alkanes and no odd over even pre-
dominance in the long-chain homologues (Table 2; Fig. 3).
The CPI close to 1.0 and the presence of a hump in the high-
molecular range argues for intense biodegradation of the fos-
sil wood.

According to Didyk et al. (1978), pristane/phytane ratios

between  1.0  and  3.0  indicate  dysaerobic  conditions  during
early diagenesis. This is in contrast to the reducing environ-
ment indicated by the even carbon number predominance of
short-chain  n-alkanes.  However,  pristane/phytane  ratios  are
also  known  to  be  affected  by  maturation  (Tissot  &  Welte
1984)  and  by  differences  in  the  precursors  for  acyclic  iso-
prenoids  (i.e.  bacterial  origin;  Volkman  &  Maxwell  1986;
ten Haven et al. 1987). In the present case, the influence of
different  ranks  on  pristane/phytane  ratios  can  be  ruled  out.

TOC EOM Saturated

HC Aromatic HC

NSO

Asphaltenes

Sample

(wt. %) (mg/g TOC) (wt. %, EOM) (wt. %, EOM) (wt. %, EOM) (wt. %, EOM)

P1/18

0.20

21.8

P1/71b

0.25

23.1

21 2 63 14

P1/198

0.20

31.6

16 6 64 14

P2/35

0.39

10.7

13 4 66 17

P2/96

0.48

14.0

16 4 71

P2/104

0.31

19.8

10 2 67 21

P2/138

0.49

11.2

15 5 76

P2/208

0.38

19.5

15 3 78

P2/247

0.74

6.1

P2/268a

0.69

8.4

P3/1a

0.25

17.2

18 2 73

P3/19

0.22

33.8

13 5 77

P2/160 FW 14.25

65.7

51 2 28 19

TOC = Total organic carbon, EOM = Extractable organic matter, HC = Hydrocarbons, NSO = NSO compounds

Table 1: Bulk organic geochemical data of sediment samples and fossil wood.

The n-alkane patterns of most sam-

ples are dominated by short-chain n-al-
kanes ( > n-C

15—19

). The short-chain

n-alkanes ( < C

), which are predomi-

nantly  found  in  algae  and  microorgan-
isms  (Cranwell  1977),  are  detected  in
high relative amounts ( > 30 % of the to-
tal n-alkane concentrations) in the sed-
iment  samples  (Table 2;  Fig. 5).  The
predominance  of  n-alkanes  with  even
carbon  numbers  (e.g.  n-C

, n-C

n-C

) indicates reducing conditions

during early diagenesis of the sedi-
ments (Welte & Waples 1973). In con-
trast, long-chain n-alkanes ( > n-C

) are

characterized by a slight odd over even

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GEOLOGICA CARPATHICA, 2012, 63, 5, 399—405

In contrast, a proportion of pristane may
be  derived  from  tocopherols  (Goossens
et  al.  1984),  or  may  simply  reflect  the
contribution  of  land  plants  to  organic
matter  accumulation  (Tissot  &  Welte
1984).  No  acyclic  isoprenoids  of  low-
molecular weight are present in the satu-
rated  hydrocarbon  fraction  of  the  fossil
wood  sample,  most  probably  due  to  in-
tense biodegradation.

Steroids

In all sediment samples, the 5 C

and C

steranes, dominating over the

corresponding  5   steranes,  are  present
in  concentrations  sufficient  for  peak  in-
tegration  (Table 2;  Fig. 3).  The  C

pseudohomologues occur in lower rela-
tive concentrations. The presence of 5
steranes is in agreement with the imma-
ture character of the samples.

Algae are the predominant primary

producers of C

sterols, while C

ste-

rols  are  more  typically  associated  with
land  plants  (Volkman  1986).  Nonethe-
less, numerous results from recent biom-
arker  studies  add  to  the  growing  list  of
microalgae that contain high proportions
of  24-ethylcholesterol  (Volkman  et  al.
1999).  The  occurrence  of  C

and C

steranes  in  the  sediments  is  consistent
with  a  mixed  origin  of  organic  matter
from  phytoplankton  and  land  plants.  In
the EOM from the fossil wood, no ster-
anes were detected.

Hopanoids

Hopanes are constituents of the non-

aromatic cyclic triterpenoids in most

n-Alkanes n-C

15–19

/ n-C

27–31

/ CPI Pristane/

Hopanes

Sesquiterpenoids Diterpenoids PAH

n-Alkanes n-Alkanes

Phytane Steranes Steranes

Steranes

(Arom.) (Arom.)

( g/g TOC)

( g/g TOC) ( g/g TOC) ( g/g TOC) ( g/g TOC)

( g/g TOC)

( g/g TOC) ( g/g TOC)

102

0.27

0.32

1.29 1.09 1.4 1.1 1.7 25.2

17.3

18.3 13.4

282

0.44

0.24

1.30 0.96 8.9 7.5 9.4 56.7

13.2

14.0 10.2

124

0.44

0.24

1.28 1.02 1.8 1.5 2.1 23.1

45.4

16.1 49.7

0.45

0.17

1.18 0.91

0.6

0.5

0.7

8.3

32.9

2.5

4.8

108

0.43

0.20

1.36 0.84

4.8

3.0

6.1

30.8

34.1

2.3

8.3

0.52

0.16

1.43 1.10

1.0

0.8

1.4

7.3

34.3

2.4

11.9

0.52

0.13

1.18 1.11

1.3

1.2

1.6

7.7

20.5

1.5

7.3

0.51

0.15

1.41 1.15

2.8

2.3

3.3

19.8

24.9

3.7

13.4

0.47

0.14

1.23 1.05

0.6

0.5

0.7

4.7

8.7

2.3

6.5

0.50

0.12

1.32 0.93

0.4

0.5

3.1

10.3

2.5

5.2

0.38

0.23

1.42 0.73

1.1

1.0

1.6

9.3

2.2

4.9

117

0.50

0.13

1.34 1.38

1.5

1.2

1.8

17.2

34.9

6.9

13.3

1970 0.00 0.32

1.04

0.0

11.3

2.4

11.4

CPI = Carbon preference index, PAH = Polycyclic aromatic hydrocarbons.

Table 2: Concentration and concentration ratios of compounds and compound groups identified in the hydrocarbon fractions of the Puez samples.

Fig. 3. Gas chromatograms (total ion current) of saturated hydrocarbon fractions of two
sediment samples (a, b), and the fossil wood (c). n-Alkanes are labelled according to car-
bon number. Std. = standard (deuterated n-tetracosane).

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NEW GEOCHEMICAL DATA ON FOSSIL WOOD FROM THE ALBIAN OF THE DOLOMITES (ITALY)

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GEOLOGICA CARPATHICA, 2012, 63, 5, 399—405

samples (Fig. 3; Table 2). The samples show similar pat-
terns, characterized by the occurrence of 17 , 21 (H)-type
hopanes from C

to C

, with C

hopanes absent. The 17 ,

21 (H) hopanes from C

to C

are present in very low

amounts. The predominant hopanoid is either the

-C

ho-

pane or the

-C

hopane. The most probable biological pre-

cursors of the hopanes are bacetriohopanepolyols (Ourisson et
al. 1979; Rohmer et al. 1992). These compounds have been
identified in aerobic bacteria and fungi, as well as in crypto-
games (e.g. ferns, moss) and, most recently, sulphate-reducing
bacteria (Blumenberg et al. 2006).

The ratio of the 22S/(22S + 22R) isomers of the 17 ,

21 (H) C

hopanes of most samples is in the range of 0.51

to 0.55, close to the equilibrium value of ca. 0.6 (Mackenzie
et al. 1982). These values argue for a thermal maturity equiva-
lent to vitrinite reflectance values around 0.5 % R

(Mackenzie

Fig. 4. Gas chromatograms (total ion current) of aromatic hydrocarbon fractions of two
sediment samples (a, b), and the fossil wood (c). Std. = standard (1.1

’-binaphthyl).

& Maxwell 1981), slightly higher than the
value of 0.4 % R

measured within the fos-

sil wood sample.

Sesquiterpenoids and diterpenoids

In all samples, sesquiterpenoid tetrahy-

drocadalene predominates in the aromatic
hydrocarbon  fractions  (Fig. 4;  Table 2).
Further  constituents  of  the  aromatic  ses-
quiterpenoids are calamenene, curcumene
and  cadalene  (Simoneit  &  Mazurek
1982).  The  aromatic  diterpenoids  present
in  the  samples  consist  of  compounds  of
the abietane-type (e.g. simonellite, retene;
Philip 1985) (Fig. 4; Table 2).

The sesqui- and diterpenoids are most

probably derived from precursor molecules
abundant in resins of conifers belonging to
the families Podocarpaceae, Araucariaceae,
and Cupressaceae (Noble et al. 1985; Otto
&  Wilde  2001).  Araucariaceae  and  Podo-
carpaceae evolved during the Early Trias-
sic  and  are  therefore  considered  as  the
most  probable  precursor  plants  for  the
sesqui- and diterpenoids found in the EOM
of the samples (Stewart 1983). In the fos-
sil  wood,  only  aromatic  sequiterpenoids
were identified.

Polycyclic aromatic hydrocarbons

The polycyclic aromatic hydrocarbon

(PAH)  phenanthrene  was  detected  in  all
samples  (Fig. 4;  Table 2).  Phenanthrene
and its methylated analogues derive from a
variety  of  non-specific  precursor  com-
pounds  such  as  steroids  and  triterpenoids
(Tissot & Welte 1984). Polycyclic aromat-
ic  hydrocarbons  (PAHs)  with  4—5  rings
ranging from fluoranthene to benz-(ghi)-pe-
rylene are present in the samples (Fig. 4).
In recent sediments, combustion products

of  fossil  fuels  represent  the  main  source  of  these  PAHs
(Laflamme  &  Hites  1978).  PAHs  in  ancient  sediments  may
result  from  wildfires  (Killops  &  Killops  1993),  or  may  be
formed  during  microbially  mediated  diagenetic  processes
(Alexander et al. 1992). Some compounds (i.e. perylene) may
derive  from  polyaromatic  precursors  synthesized  by  living
organisms such as fungi (Tissot & Welte 1984).

The PAHs present in the samples and the absence of their

methylated  analogues  argue  for  the  origin  of  these  com-
pounds from charcoal and/or an input of PAHs attributed to
recurring  forest  or  swamp  fires.  However,  as  outcrop  sam-
ples  are  being  investigated  here,  an  anthropogenic  source
(i.e. combustion products of fossil fuels) cannot be excluded.
Furthermore, perylene is the dominating compound in most
samples. For this PAH, a variety of biological sources have
been considered.

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GEOLOGICA CARPATHICA, 2012, 63, 5, 399—405

Conclusions

Drift-wood is reported for the first time from the Lower

Cretaceous  of  the  Southern  Alpine  region.  According  to  its
terpenoid  hydrocarbon  composition,  the  wood  fragment  de-
rived from a conifer belonging to the family Podocarpaceae
or  Araucariaceae.  The  age  of  the  drift-wood  is  assigned  to
the  Mid-Albian  on  the  basis  of  the  foraminifera  fauna.  The
wood  derives  from  surrounding  islands  formed  during  the
beginning  of  the  Alpine  orogeny.  The  fossil  wood  was  de-
posited  after  considerable  drifting  onto  the  sea-floor  of  the
Albian Trento Plateau. Long-term drifting is indicated by the
infestation of the bivalve Teredo (“shipworm”) and by the in-
tense degradation of the organic matter (OM). Other boring
organisms,  probably  worms,  are  indicated  by  fecal  pellets,
confiming the long term drifting hypothesis.

Acknowledgments: Thanks are due to the Austrian Science
Fund  (FWF)  for  financial  support  (Project  P20018-N10).
Sincere thanks go to Evelyn Kustatscher, Benno Baumgarten
and  Vito  Zingerle  (all  Museum  of  Nature  South  Tyrol)  for
their help in organizational issues. I thank Arthur Kammerer,
Astrid Wiedenhofer and Valentin Schroffenegger (all Office
for  Natural  Parks  South  Tyrol)  for  working  permits  in  the
Puez-Geisler Nature Park. Preparation work on the rock sam-
ples  and  thin  sections  was  done  by  Anton  Englert  (Vienna)
and Franz Topka (Vienna). Photographs were taken by Alice
Schumacher (Vienna).

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