Determination of the molecular signature of fossil conifers by experimental palaeochemotaxonomy.
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Transcript of Determination of the molecular signature of fossil conifers by experimental palaeochemotaxonomy.
Determination of the molecular
signature of fossil conifers by
experimental
palaeochemotaxonomy.
Contribution to palaeofloristic and
palaeoclimatic reconstructions.Y. Hautevelle*, R. Michels, B. Farre, F. Lannuzel, F. Malartre
* UMR G2R 7566, Université Henri Poincaré, Vandoeuvre-lès-Nancy, France Current address : UMR 7509, Laboratoire de Chimie Bioorganique, Strasbourg, France
Botanical chemotaxonomyIntro-duction
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Terpenoids have a chemotaxonomic value and are
thus specific of certain taxa
Chemical composition :- lignin- carbohydrates- lipids, e.g. terpenoids
conifers
Abietic acid
angio-sperms
lupeol
From bioterpenoids to geoterpenoidsIntro-duction
BIOSPHERE
GEOSPHERE
Sedimentary basin
transport
sediment
bioterpenoids
Geoterpenoids can keeptheir initial
chemotaxonomic value
conifers
angio-sperms
Geoterpenoids ormolecular biomarkers
Diagenetic
transformations
angio-sperms
conifers
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Distribution of plantbiomarkers
Palaeofloristic compositionon emerged lands
Intro-duction Palaeofloristic and palaeoclimatic reconstructions
The distribution of plant biomarkers reflect the palaeofloristic composition during the deposition
cypres
fern
Interpretation in terms of palaeofloristic composition
pine pineangio-
sperms
sequoia
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Intro-duction
desertic climate
temperate climate
tropical climate
polar climate flora ↔ climate
Relations between floras and climates
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Chemostratigraphy of vascular plant biomarkersIntro-duction
stratigraphic record
palaeobiodiversitypalaeoflora
palaeoclimateT°, humidity
desertic climate
temperate climate
molecular facies
Geolo
gic
al ti
mes
tropical climate
Plant biomarkers : Are they really interesting compared to other proxies ?
Do they really bear pertinent information ?Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Advantages of palaeochemotaxonomy
but fossils are scarse
Improved approaches for palaeofloristic
and palaeoclimatic reconstructions
PALAEOBOTANY(fossil plants)
PALYNOLOGY(spore & pollen)
but spores & pollen are not easily reliable to plant taxa
BOTANICAL PALEOCHEMOTAXONOMY (plant biomarkers)
-widespread in the sedimentary record
- related to plant taxa if they have a palaeochemotaxonic value
however plant biomarkers are :
BUT, our current knowledge in paleochemotaxonomyis weak and very lacunar
Intro-duction
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Aims of experimental palaeochemotaxonomy
plantbiomarkers
palaeofloristic and palaeoclimatic proxies
➜ new technique of artificial maturation of living plants (confined pyrolysis).
➜ experimental "reproduction" of the plant diagenesis & fossilisation (at the molecular scale).
➜ Aim :
Moleculartaxonomy
Botanicaltaxonomy
I.01
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
I.02 Experimental and analytical procedures
Fresh plant Sealed gold tubes Confinedpyrolysis
Solubilisation ofterpenoids (CH2Cl2)
Molecular analysis(GC-MS)
Aliphatic
Aromatic
Polar
FractionationConclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
I.03 Development of experimental palaeochemotaxonomy
Diagenesis of bioterpenoids : ➜ progressive removal of oxygenated functions
➜ reduction of double bonds ➜ saturation vs. aromatisation of 6C cycles (depending on redox conditions
during diagenesis)
Experimental diagenesis : ➜ in accordance with these transformations ➜ generate the broadest possible distribution of biomarkers
(functionalised & hydrocarbon ; aromatic & saturate)
Development of the pyrolysis procedure :
➜ well known diagenetic pathway of a bioterpenoid
➜ abietanoic acids like abietic acid
Diagenetic pathway of abietanoic acids
Laflamme and Hites, 1978 ; Wakeham et al., 1980; Simoneit, 1986; Otto and Simoneit, 2001, 2002; Marchand-Genest and Carpy, 2003, etc.Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Choice of the plant and its initial compositionII.01
Fresh Abies pinsapoMethylated total fraction
Retention time
Diagenetic pathway of abietanoic acids
Fresh Abies pinsapo contains large amounts
of abietanoic acids
Abies pinsapo (Spanish fir)
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
II.02
150°C
200°C
250°C
280°C
300°C
Other pyrolysis parameters :duration : 24 h ;pressure : 700 bars.
Diagenetic pathway of abietic acid
280°C Presence ofaromatic diterpanes
Pyrolysed Abies pinsapoTotal fractionm/z 219, 223, 237, 239, 241
Determination of the ideal pyrolysis temperature
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
II.03
phytene
280°C
280°C presence of diterpanesclassically detected
in the geosphereLiAlH4
Unsaturated abietanes
not satisfying
Pyrolysis with LiAlH4
Pyrolysed Abies pinsapoAliphatic fraction TIC
280°CSaturatedabietanes
labdanes
Diterpane diagenesis
Pyrolysed Abies pinsapoAliphatic fraction TIC
Generation of saturated diterpanes
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
II.04Pyrolysed Abies pinsapoAliphatic fraction TIC
Pyrolysed Abies pinsapoAromatic fraction TIC
pyrolysed Abies pinsapoPolar fraction TIC
with LiAlH4
280°C
WithoutLiAlH4
280°C
withoutLiAlH4
280°C
Palaeochemotaxonomy of a virtual fossil Abies pinsapo
Typical molecular signature of fossil
Pinaceae
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
II.05
Aliphatic fractionTime : 24 h, pressure : 700 bar, temperature : 280°C, WITH LiAlH4
Aromatic fractionTime : 24 h, pressure : 700 bar, temperature : 280°C, WITHOUT LiAlH4
Polar fractionTime : 24 h, pressure : 700 bar, temperature : 280°C, WITHOUT LiAlH4
Determination/prediction of the molecular signature of the fossil counterpart of the
pyrolysed plant
The reproduction of this procedure on a great number of plant taxa should considerably increase
our knowledge in palaeochemotaxonomy
Summary of the experimental procedure
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Conifers currently studied
Coniferal order is composed of 7 familiesAraucariaceae
3 Agathis, 8 Araucaria & 1 Wollemia
Cupressaceae1 Calocedrus, 4 Chamaecyparis, 2 Cupressus, 5 Juniperus,
1 Microbiota, 3 Thuja & 1 Thujopsis
Pinaceae 4 Abies, 3 Cedrus, 4 Larix, 5 Picea, 4 Pinus, 1 Pseudotsuga &
1 Tsuga
Podocarpaceae4 Podocarpus
Sciadopityaceae1 Sciadopitys
Taxaceae2 Taxus, 2 Cephalotaxus, 1 Torreya
Taxodiaceae 1 Cryptomeria, 2 Cunninghamia, 1 Sequoiadendron, 1 Meta-
sequoia, 1 Sequoia & 2 Taxodium
69 species studied forexperimental palaeochemotaxonomy
III.01
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Example of Araucariaceae (sesquiterpenoids)
Araucariaangustifolia
Araucariaaraucana
Araucarialaubenfelsii
n-C14 n-C15
Aliphatic fraction Aromatic fraction
farnesane
bisabolanes cadalanescadalenepentaMedi
hydroindenes
chamazulene ?
curcumenes
III.02
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
III.03
Araucariaangustifolia
Araucariaaraucana
Araucarialaubenfelsii
labdanes
(iso)pimaranes
MonoaromaticLabdane ?
Monoaromatictetracyclic diterpane
Aromaticabietanes
Aliphatic fraction Aromatic fraction
Example of Araucariaceae (diterpenoids)
beyerane
phyllocladaneskauranes
phyllocladanes
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Results on the whole Coniferale orderIII.04
AraucariaceaeHigh abundance of tetracyclic diterpanes
Low abundance of tricyclic diterpanes & polar terpenoids
CupressaceaeHigh diversity between the different genera
Cuparene, cedrane and totaranes seem specific
Systematic occurrence of ferruginol and occasional occurrence of tetracylic diterpanes
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
PinaceaeSystematic presence of dehydroabietic acid and dehydroabietol
Some fonctionnalised compouds seem to be specific for some genera
TaxodiaceaeHigh diversity between the different genera
Presence of ferruginol & sugiol
Occasional occurrence of tetracyclic diterpanes
Results on the whole Coniferale orderIII.05
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Difficulties of experimental palaeochemotaxonomyIV.01
Huge mass of data acquired on 69 species of conifers
Fresh plants
pyrolysed plants (with & without LiAlH4)
Presented data "Iceberg's point"
many information remainsto be discovered
a lots of compounds have never been
reported and remain to be identifed
Many peaks "orphan" spectra➜
Their future identification will supply much more
palaeochemotaxonic dataConclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Future identification of unknown biomarkersIV.02
Araucariaangustifolia
Aromaticfraction
Monoaromatictetracyclic diterpane
?M+ : 240 ➜ C18H24
Loss of 5 C atoms on
cycles D & E
Ellis et al. (1996)pyrolysis of pure compounds
pyrolysis of commercial essential oils
pyrolysis of commercial resinsConclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Perspectives of experimental palaeochemotaxonomyIV.03
Enlarge on other botanical groups :
- Angiosperms ;
- Bryophytes, pteridophytes (as ferns)and cycadophytes.
In targeting the organisms which have a palaeoenvironmental interest
Enlarge on other living organisms :
- Bacteria (anoxygenic, psychrophile bacteria, cyanobacteria, etc…)
- Planktonic organisms ;
- Animals, etc…
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
ConclusionsConclusion
Experimental Palaeochemotaxonomy ➜ pertinent and innovative approach
investigate the molecular composition of fossil plants from their present
representatives
BOTANICAL PALAEOCHEMOTAXONOMY(plant biomarkers)
PALEOBOTANY(fossil plants)
PALYNOLOGY(spore & pollen)
Molecularsystematic
Botanicalsystematic
Conclusions
II. Developmentof experimental
palaeochemotaxonomy
Introduction
IV. Perspectives& future works
I. Objectives& procedure ofexperimentalpalaeochemo
taxonomy
III. Applicationto Coniferales
Y. HautevelleR. Michels, B. Farre, F. Lannuzel, F. Malartre
Determination of the molecular signature of fossil conifers by experimental
palaeochemotaxonomy.
Contribution to palaeofloristic and palaeoclimatic reconstructions.