Chapter 0 - Syllabus and Introduction · Kapitel 2 –Molekulare Diagenese und Catagenese Molecular...
Transcript of Chapter 0 - Syllabus and Introduction · Kapitel 2 –Molekulare Diagenese und Catagenese Molecular...
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Vorlesung „Organische Geochemie“ in B201
Komplementäre Vorlesungen und Vorkenntnisse
Chapter 0 - Syllabus and Introduction
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B101 – Einführung in die Geowissenschaften
B103 – Einführung in die Erdgeschichte und Biologie
B405 – Krisen der Evolution
B201 – Chemie organischer Naturstoffe, GeochemischeAnalytik
B403 – Isotopengeochemie, Chemische Ozeanographie,Stoffkreisläufe
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Konzept „Organische Geochemie“
Biomoleküle werden von Organismen spezifisch (enzymatisch)
hergestellt, um bestimmte Funktionen zu erfüllen, die dem Habitat
und der Lebensweise sowie dem Evolutionsgrad der Organismen
entsprechen. Biomoleküle besitzen daher chemotaxonomische
Relevanz und bilden die Lebensumwelt von Organismen ab.
Nach dem Absterben von Organismen wird der überwiegende Teil
ihrer Biomasse rezyklisiert und in Stoffkreisläufe zurückgeführt.
Unter geeigneten Bedingungen kann ein geringer Teil der Biomasse
in der Geosphäre erhalten bleiben, wobei der überwiegende Anteil
diagenetisch in das partikuläres Geomakromolekül „Kerogen“
überführt wird. Dieses kann in seiner Pauschalzusammensetzung
nur bedingt Aufschluss über den biologischen Eintrag und die
Paleoumweltbedingungen seiner Entstehung liefern.
Chapter 0 - Syllabus and Introduction
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Konzept „Organische Geochemie“
Ein geringer Teil des in der Geosphäre erhaltenen organischen
Materials wird nicht in das Kerogen eingebaut sondern behält bei
nur geringer chemischer Veränderung seine biologisch-molekulare
Identität, d.h. biologisch angelegte Molekülstruktur.
Derartige Geomoleküle werden als „Biomarker“ oder „molekulare
Fossilien“ bezeichnet, da sie unter Erhalt ihrer Primärstruktur
(Kohlenstoffskelett) auch nach Defunktionalisierung (Entfernung
funktioneller Gruppen, d.h. reaktiver Molekülteile) sowie geringer
und nachvollziehbarer chemischer Veränderung (Isomerisierung)
ihre Herkunft von spezifischen Biomolekülen anzeigen.
Über das Aktualismusprinzip und komplementäre Techniken lassen
sich über Biomarker die Bioproduzenten, deren Umweltansprüche,
die Fazies des Ablagerungsraums und die (thermische) Diagenese
der Sedimente rekonstruieren.
Chapter 0 - Syllabus and Introduction
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Biological indicators in recent und fossil systems
Makrofossils Mikrofossils Molecular Fossils
Macroorganisms Microorganisms Biomolecules
Ju
rass
ic
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910
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1415
16
1718
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2021 22
2324
25
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Stigmastenol
29
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910
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2021 22
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Stigmastane
Ju
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Chapter 0 - Syllabus and Introduction
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Biomolecules following minor diagenetic alteration are preserved in
the Geosphere allowing for reconstruction of fossil environments and
processes
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Chapter 0 - Syllabus and Introduction
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Chapter 0 - Syllabus and Introduction
The Tree of Life
DNA the biggest and most detailed biomarker molecule.
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Chapter 0 - Syllabus and Introduction
The Tree of Life
How reliable is DNA as a biomarker? Specificity is excellent but signal preservation over geological time scales is very problematic.
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Chapter 0 - Syllabus and Introduction
The Tree of Life
Evolutionary branching points based on 16rRNS analyses of Recent organisms.
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Chapter 0 - Syllabus and Introduction
The Tree of Life - its Biochemicals
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Chapter 0 - Syllabus and Introduction
The Tree of Life - its Biomarkers
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Chapter 0 - Syllabus and Introduction
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Chapter 0 - Syllabus and Introduction
Specific Membrane Tetraether Lipids
Archaea – C86 Bacteria – C66+
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Chapter 0 - Syllabus and Introduction
Specific Membrane Tetraether Lipids
GDGT-Tetraether lipidprofiles determined byLC-APCI-MS for threedifferent soils:
a) arable soil (barley field)b) non-managed grasslandc) managed grassland
Cal= CaldarchaeolCren= CrenarchaeolBIT= branched isoalkane
tetraether
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Chapter 0 - Syllabus and Introduction
Applications of Organic and Isotope Geochemistry in:
• Environmental Analyses
• Petroleum Geology
• Organismic Evolution
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Chapter 0 - Syllabus and Introduction
Environmental Analyses - Archives
Polycyclische aromatische Kohlenwasserstoffe
(PAK)
Verbrennungsprodukte• Verkehr
• Hausbrand
• Stromerzeugung
• Industrie
natürliche Quellen
Diagenese
Fossile Brennstoffe
Andere PAK-Quellen
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Chapter 0 - Syllabus and Introduction
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Chapter 0 - Syllabus and Introduction
Environmental Analyses - Archives
178
178
202
202
228
228
228252
252
252
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Chapter 0 - Syllabus and Introduction
Environmental Analyses - Archives
Source identification
0 0.5 1 1.5 2
Fla/Py
0
10
20
30
40
50
60
P/A
1.1 1.2 1.3 1.4 1.5 1.6 1.7
Fla/Py
4
5
6
7
8
1957-1998
1934-1956
1932
petrogen
pyrogen
PAH isomer distribution depends on PAH formation temperature:a) Low temperature and/or long reaction time -> petrogenicb) High temperature and/or short reaction time -> pyrogenic
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Chapter 0 - Syllabus and Introduction
Environmental Analyses - Archives
Source identification
perylene
-24,92 /0
00
-28,55 /0
00
0.1 1 10 100
perylene-ra tio
d13C=
d13C=
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Chapter 0 - Syllabus and Introduction
Environmental Analyses - Archives
0 40 80 120 160
PAK
[ µg/g ]
1930
1940
1950
1960
1970
1980
1990
2000
4 8 12
PCB
[ µg/g ]
2000 4000
aliph. NKG
[ µg/g ]
0 10 20 30 40 50
Hopan
[ µg/g ]
2 4 6 8 10
LAB
[ µg/g ]
0 4 8 12
[
TPB
µg/g ]
V
IV
I I I
I I
I
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Chapter 0 - Syllabus and Introduction
Environmental Analyses
Oil Spills
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Kapitel 8 - Environmental Geochemistry and Oil Spills
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Kapitel 8 - Environmental Geochemistry and Oil Spills
Exxon Valdez Oil Spill
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Kapitel 8 - Oil Spills
Exxon Valdez Oil Spill
Original Exxon Valdez crude (EVC) total petroleum hydrocarbon (TPH) composition and weathered EVC tar collected on Peak Island, 1993.
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Kapitel 8 - Oil Spills
Exxon Valdez Oil Spill
Composition of TPH derived from anthropogenic sources unrelated to the Exxon Valdez accident. Californian oils had been imported to Alaska since the late 19th century to support fishing and canning as well as mining industry.
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Kapitel 8 - Oil Spills
Exxon Valdez Oil Spill
Composition of TPH derived from natural sources in the PWS area which are unrelated to Exxon Valdez accident.
Based on TPH chromatograms sourceidentification and allocation is not feasible.
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Kapitel 8 - Oil Spills
Exxon Valdez Oil Spill
Diagnostic ratios of aromatics versus thioaromatics differentiate EVC from: natural seepage, local oil production, ANS diesel, pre-spill-cores (local and Californian signatures).
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Kapitel 8 - Oil Spills
Exxon Valdez Oil Spill
Weathering drastically changes ratios of light versus heavy PAH components but the diagnostic ratios of aromatics versus thioaromatics remain constant due to similar vapor pressures
and susceptibilty towards biodegradation and photolysis.
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Chapter 0 - Syllabus and Introduction
Environmental Analyses
Air Quality
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Schw
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Chapter 8 – Case study – Air quality in the Cologne Conurbation
Cologne Conurbation - Accumulation
10 µm
SEM-EDX for identification of particle composition Urbat et al. (2004)
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Schw
ar
k &
Lehndo
rff –
ISPAC
2007
Tro
ndh
eim
Cologne
Dueren
Euskirchen
Bonn
Cologne Conurbation – Total PAH
Sch
war
k –
Bio
monit
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nvir
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oll
uti
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Chapter 8 – Case study – Air quality in the Cologne Conurbation
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Transport Fractionation of PAHS
chw
ark –
Bio
monit
ori
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oll
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Chapter 8 – Case study – Air quality in the Cologne Conurbation
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Schw
ar
k &
Lehndo
rff –
ISPAC
2007
Tro
ndh
eim
Traffic-related PAH Patterns
9/1mPCPcdP
CPP Fluo / Py
Sch
war
k –
Bio
monit
ori
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n E
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oll
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Chapter 8 – Case study – Air quality in the Cologne Conurbation
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Dd13C
CuSb
Traffic-related non-PAH indicators
K d13C
Cu
Sch
war
k –
Bio
monit
ori
ng i
n E
nvir
onm
enta
l P
oll
uti
on
Chapter 8 – Case study – Air quality in the Cologne Conurbation
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Sb
Traffic-related non-PAH indicators
Ru
Pt
Pd
Sch
war
k –
Bio
monit
ori
ng i
n E
nvir
onm
enta
l P
oll
uti
on
Chapter 8 – Case study – Air quality in the Cologne Conurbation
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Chapter 0 - Syllabus and Introduction
Petroleum Geology
Maturity Parameters
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Kapitel 2 – Molekulare Diagenese und Catagenese
Molecular Maturity Parameters - Geomarker
Maturity sequence of alkylated naphthalenes.
low maturitymoderate maturity
high maturity
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Kapitel 2 – Molekulare Diagenese und Catagenese
Molecular Maturity Parameters
Hopanoid biomarker variation with increasing thermal stress. Isomerism within the triter-penoid side chain yields 22S from 22R-hopanes upon continuous burial depth.
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Kapitel 2 – Molekulare Diagenese und Catagenese
Molecular Maturity Parameters
Steroid biomarker variation with increasing thermal stress. Isomerism within the steroid side chain yields 20S from 20R-steranes upon continuous burial depth.
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Kapitel 2 – Molekulare Diagenese und Catagenese
Molecular Maturity Parameters
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Kapitel 2 – Molekulare Diagenese und Catagenese
Molecular Maturity Parameters - Korrelation
Various molecular thermal maturity ratios correlated
with bulk/total OM (non-molecular)
maturity indicators.
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Chapter 0 - Syllabus and Introduction
Molecular Evolution
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L. Schwark Molekulare Evolution, Paläoklima, Stoffkreisläufe
Algenevolution
A phylogenetic distribution of terrestrial and aquatic photo-autrophs based on morphologicalcharacteristics. The deep phylogenetic diversity in aquatic photoautotrophs contrasts with that of terrestrial plants, which are overwhelmingly dominated by one clade (the Embryophytes).
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L. Schwark Molekulare Evolution, Paläoklima, Stoffkreisläufe
Algenevolution – Paläozoische SteraneDiversifizierung der Algen im Paläozoikum läßt sich über Mikrofossilien allein nicht verfolgen, da viele Arten keine überdauerungsfähigen Hartteile aufbauen. Steroide stellen Zellwandmembranbestandteile der Algen dar und ihre zeitliche Variation gibt Auskunft über Diversifizierungstrends.
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L. Schwark Molekulare Evolution, Paläoklima, Stoffkreisläufe
Algenevolution – Paläozoische SteraneRelative Verteilung der C28/C29 Sterane zeigt Zunahme während kurzlebiger biotischer Events durch Massenauftreten von “Disaster Spezies”. Bleibender Anstieg des Ratios auf >0,55 tritt erst ab dem Hangenbergevent oder der D/K-Grenze auf und indiziert grundlegende Umstellung der Algenassoziation.
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L. Schwark Molekulare Evolution, Paläoklima, Stoffkreisläufe
Algenevolution – Mesozoische Diatomeen
Phylogenie basierend auf kompletter 18S-rDNA Sequenzierung der Diatomeen. Diatomeen nicht, positiv und negativ getestet auf HBI. Diatomeen von nur 2 phylogenetische Clustern entwickeln unabhängig die Fähigkeit, HBI zu synthetisieren.
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L. Schwark Molekulare Evolution, Paläoklima, Stoffkreisläufe
Algenevolution – Mesozoische Diatomeen
Relative Konzentration von HBI in Ölen (ppm) und Sedimenten (normalisiert auf Phytan) zeigt ein Erst-Auftreten bei 91.5 Ma.
Der rapide Anstieg der rhizoselenoiden Diatomeen wurde durch eine Umstellung des Nährstoffhaushalts im kretazischen Nord-Atlantik ausgelöst. Der Nordatlantik fungierte zu Beginn der Oberkreide als stark stratifizierte Nährstofffalle, die die Verfügbarkeit von Si sehr einschränkte.
Plattentektonische Prozesse der weiteren Öffnung und Vertiefung des Nordatlantik-Gateways zum Proto-Südatlantik lösten eine Nährstoffrevolution im Oberflächen-wasser des Atlantik aus, die eine rasche Entwicklung Si-testater Algen begünstigte.
Die Kalkulation “molekularer Uhren” ging für Diatomeen von 1% pro 18-26 Ma aus. Infolge der hervorragenden Datierung konnte für rhizoselenoide Diatomeen die Evolutionsrate pro 1% auf nur 12 Ma korrigiert werden.