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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) iii–iv

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Special Issue

Organic-carbon-rich sediments through the Phanerozoic: Processes, progress, and perspectives

Edited by
A. Negri a, A. Ferretti b, T. Wagner c, P.A. Meyers d

a
Dipartimento di Scienze del Mare, Università Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy
b
Dipartimento di Scienze della Terra, Università degli Studi di Modena e Reggio Emilia, Largo S. Eufemia, 41100 Modena, Italy
c
Department of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK
d
Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan, 48109-1005, USA

CONTENTS

Publisher’s note . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Prefaces
Organic-carbon-rich sediments through the Phanerozoic: Processes, progress, and perspectives
A. Negri, A. Ferretti, T. Wagner and P.A. Meyers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
Phanerozoic organic-carbon-rich marine sediments: Overview and future research challenges
A. Negri, A. Ferretti, T. Wagner and P.A. Meyers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218

Research Papers
Transport and depositional process of soil organic matter during wet and dry storms on the Têt inner shelf (NW Mediterranean)
J.-H. Kim, R. Buscail, F. Bourrin, A. Palanques, J.S. Sinninghe Damsté, J. Bonnin and S. Schouten . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
Geochemical evidence for high-resolution variations during deposition of the Holocene S1 sapropel on the Cretan Ridge, Eastern Mediterranean
G. Gennari, F. Tamburini, D. Ariztegui, I. Hajdas and S. Spezzaferri . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Role of sea-level forced sedimentary processes on the distribution of organic carbon-rich marine sediments: A review of the Late
Quaternary sapropels in the Mediterranean Sea
R. Capozzi and A. Negri. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Benthic environmental changes in the Eastern Mediterranean Sea during sapropel S5 deposition
C. Morigi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
Organic geochemistry and paleoenvironment of the Early Eocene ‘‘Pesciara di Bolca’’ Konservat-Lagerstätte, Italy
L. Schwark, A. Ferretti, C.A. Papazzoni and E. Trevisani . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Geochemical environment of the Coniacian–Santonian western tropical Atlantic at Demerara Rise
C. März, B. Beckmann, C. Franke, C. Vogt, T. Wagner and S. Kasten . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
Paleo-redox conditions during OAE 2 reflected in Demerara Rise sediment geochemistry (ODP Leg 207)
A. Hetzel, M.E. Böttcher, U.G. Wortmann and H.-J. Brumsack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
Abstract of ‘‘Climate-Ocean coupling off North-West Africa during the Lower Albian: The Oceanic Anoxic Event 1b’’
P. Hofmann, I. Stüsser, T. Wagner, S. Schouten and J.S. Sinninghe Damsté . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
Temperature controlled deposition of early Cretaceous (Barremian–early Aptian) black shales in an epicontinental sea
J. Mutterlose, S. Pauly and T. Steuber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
Late Pliensbachian–Early Toarcian (Early Jurassic) environmental changes in an epicontinental basin of NW Europe (Causses area, central
France): A micropaleontological and geochemical approach
S. Mailliot, E. Mattioli, A. Bartolini, F. Baudin, B. Pittet and J. Guex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 346
Abstract of ‘‘The role of sea-level change and marine anoxia in the Frasnian–Famennian (Late Devonian) mass extinction’’
D.P.G. Bond and P.B. Wignall . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
Black shale deposition in an Upper Ordovician–Silurian permanently stratified, peri-glacial basin, southern Jordan
H.A. Armstrong, G.D. Abbott, B.R. Turner, I.M. Makhlouf, A.B. Muhammad, N. Pedentchouk and H. Peters . . . . . . . . . . . . . . . . . . . . . . . 368

doi:10.1016/S0031-0182(09)00059-5
iv Special Issue

Palynology, organic geochemistry and carbon isotope analysis of a latest Ordovician through Silurian clastic succession from borehole
Tt1, Ghadamis Basin, southern Tunisia, North Africa: Palaeoenvironmental interpretation
M. Vecoli, A. Riboulleau and G.J.M. Versteegh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
Organic-carbon deposition and coastal upwelling at mid-latitude during the Upper Ordovician (Late Katian): A case study from the
Welsh Basin, UK
T.J. Challands, H.A. Armstrong, D.P. Maloney, J.R. Davies, D. Wilson and A.W. Owen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) v

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Publisher's note

We regret that owing to an oversight on our part two papers
handled by the Guest Editors and accepted for inclusion in the
special issue on Organic-carbon-rich sediments through the Phaner-
ozoic: Processes, progress, and perspectives have been published
already:
D.P.G. Bond and P.B. Wignall, The role of sea-level change and
marine anoxia in the Frasnian-Famennian (Late Devonian) mass
extinction, Palaeogeography, Palaeoclimatology, Palaeoecology 263,
2008, 107-118, doi:10.1016/j.palaeo.2008.02.015.
P. Hofmann, I. Stüsser, T. Wagner, S. Schouten, J.S. Sinninghe Damsté,
Climate-Ocean coupling off North-West Africa during the Lower Albian:
The Oceanic Anoxic Event 1b, Palaeogeography, Palaeoclimatology,
Palaeoecology 262, 2008, 157-165, doi:10.1016/j.palaeo.2008.02.014.
We apologise to the authors, Guest Editors and readers for the
inconvenience caused by this. In the special issue abstracts of these
papers are included, to indicate their place in the sequence of papers.
The Publisher

doi:10.1016/S0031-0182(09)00054-6
 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 213–217

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Preface

Organic-carbon-rich sediments through the Phanerozoic: Processes, progress,

and perspectives
A. Negri a,⁎, A. Ferretti b, T. Wagner c, P.A. Meyers d
a
Dipartimento di Scienze del Mare, Università Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy
b
Dipartimento di Scienze della Terra, Università degli Studi di Modena e Reggio Emilia, Largo S. Eufemia, 41100 Modena, Italy
c
School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK
d
Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan 48109-1005 USA

a r t i c l e i n f o

Article history:
Received 3 October 2008
Received in revised form 4 November 2008
Accepted 13 November 2008

1. Introduction by “Causes and Consequences of Marine Organic Carbon Burial Through

This Special Issue is comprised of two related components. First,
we present a summary of the occurrences of organic-carbon-rich
sedimentary sequences in the Phanerozoic geological record and our
overview of the evolution and current status of understanding of how
they accumulated. We note especially some of the new advances in the
kinds of palaeoceanographic proxies that can be used and in the more
refined explanations that have emerged from these advances. The
second and greater part of the Special Issue consists of fourteen
research papers that provide examples of the more detailed analyses
of organic-carbon-rich sedimentary sequences that can be achieved
with modern techniques and that can be elegantly interpreted by
specialists in these techniques.
The stimulus for this Special Issue emerged from a very successful
topical session presented at the European Geophysical Union Meeting in
Vienna, Austria, in April 2007. The very well attended (80–100 people)
session addressed recent research advances in “Organic-carbon rich
sediment through time: Past present and future, ocean and climate
feedback” that included a large number of excellent oral and poster
presentations. This session was the continuation of a project started in
2000 that has already yielded two well-received special issues of Palaeo-
geography, Palaeoclimatology, Palaeoecology. Both special issues present
collections of contributions that deal with organic-carbon-rich marine
sequences in different temporal windows, and both simultaneously
emphasize new issues in research and reviews of existing concepts and
models. The current volume forms a trilogy launched by the Special Issue
“Paleoclimatic and Paleoceanographic Records in Mediterranean Sapro-
pels and Mesozoic Black Shales” (Meyers and Negri, 2003) and continued
⁎ Corresponding author.
E-mail address: a.negri@univpm.it (A. Negri).
Time” (Negri et al., 2006). These two volumes brought together the
sapropel and black shale communities that had previously studied these
organic-carbon-rich sequences separately. Moreover, their goal was to
highlight the similarities and differences of these two kinds of interesting
sediments, pointing to mergers of the knowledge acquired separately (e.g.,
Meyers, 2006).
With the current Special Issue we expand the coverage of geological
time to include the Palaeozoic Era to explore the processes involved in
deposition of organic-carbon-rich sequences in this huge interval of
deep time (291 Ma). Investigators of Palaeozoic settings must cope with
the problems of lower time resolution, seldom continuous outcrops, and
general lack of undisturbed deep sea sediment sequences. Study of all
palaeoceanographic processes is necessarily mediated by the available
time resolution, and in the Palaeozoic the length of individual biozones
is generally on the order of millions of years, which is in the same range
as third-order sea-level changes. Thus, an important question in
Palaeozoic sequences is whether episodes occur at different scales or
belong to cycles of diverse order. Nevertheless, the study of these very
old sediments cannot be neglected because they represent intervals of
time that are characterized by cycling of tremendous amounts of CO2,
which is one of the main factors responsible for profound changes in the
Earth–Ocean–Atmosphere system and whose increase is central to
modern climate changes.
Within this broad framework, a combined geochemical, palaeontolo-
gical, and biological approach can address prominent examples in Earth
history to assess the mechanisms operating during natural rapid global
change either in greenhouse (e.g., the Cretaceous) or icehouse (e.g.,
Pliocene–Pleistocene) conditions. Better integration of observations of
past and current climatic conditions can considerably enhance our global
understanding of basic aspects of the ocean carbon system and associated
climate change. In addition, a growing recognition exists that the concepts
and models that have been proposed to explain how organic-carbon-rich

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.11.016
214 Preface

Fig. 1. Organic carbon-rich sediments through time (Photo credits: Petr Štorch, A.N., T.W. and ISMAR CNR Bologna). A: Holocene sapropel S1 in the Ionian Basin. B: The most
spectacular outcrop of pelagic Cretaceous sediments in the Umbria Marche Basin of Italy: the Vispi Quarry in the Contessa Valley, near Gubbio. Sediments span 80 My and belong to
four formations: Maiolica, Marne a Fucoidi, Scaglia Bianca, and Scaglia Rossa. The Marne a Fucoidi Fm. (MaF) shows evident cyclic alternations of light carbonate rich marls and darker
shales related to Milankovitch orbital perturbations. Arrow indicates the Selli Level (OAE1a, late early Aptian). C: Coastal exposure of upper Cenomanian marl-black shale sequences
at Mohammed Plage, North of Tarfaya, southern Morocco. Alternations of light colour carbonate-rich marls and dark organic carbon-rich black shale document regular changes in
environmental and climatic conditions that occurred at orbital frequencies. D: Close-up of organic carbon-rich black shales showing mm-scale lamination indicative of extreme
oxygen depletion at the time of deposition. E: Prague Basin, Kosov Quarry, Silurian black shales of the Motol Formation (Wenlock, ramosus-ellesae and lundgreni graptolite biozones).

marine sediments are deposited merit reconsideration. Are there other
mechanisms for organic carbon preservation that are viable alternatives to
the classical anoxia vs. productivity models?
The challenge therefore is to understand if the scientific community,
notwithstanding their respective specialization in different time windows,
can come to a common language and a common system that can
disentangle critical elements of the earth history puzzle. This new
knowledge will directly impact our ability to make realistic future
projections beyond the human-scale time horizon and to assess potential
carbon management scenarios, and it will represent a fundamental source
of information about possible future oceanic responses to a progressively
warming world. Recent observations in the equatorial Atlantic and Indian
oceans that support decreasing oxygenation of the tropical ocean
(Stramma et al., 2008) highlight the urgency of this topic and emphasize
immediate demand for integrated research strategies.
1.1. Note
Two papers that should have been included in this Special Issue
were by mistake published before (Bond and Wignall, 2008; Hofmann
 Preface
Table 1
Main features of the papers included in this special issue
et al., 2008). In their place in this issue (extended) abstracts are in-
cluded (Bond and Wignall, 2009-this issue; Hofmann et al., 2009-this
issue).
2. Organization and content of the research papers
The fourteen contributions to this Special Issue on organic-carbon-
rich sedimentation are organized by increasing geological age (see
Table 1). Although this order is the reverse of how the sequences were
deposited, we elected it for two reasons. First, recent and near-recent
sequences are more easily studied in detail than older and often less-
complete sequences. Second, the Pliocene–Pleistocene sapropels of
the Mediterranean Sea are increasingly being considered as near-
modern analogs of Mesozoic and Palaeozoic black shales. Under-
standing the palaeoceanographic and palaeoclimatic processes that
led to sapropel deposition therefore can improve understanding of
how older organic-carbon-rich sequences were deposited. The range
of geological ages that the fourteen contributions span is from the
modern to the Ordovician. The papers are consequently grouped into
Cenozoic, Mesozoic, and Palaeozoic units.
The Cenozoic unit of this Special Issue begins with a study by Kim
et al. (2009-this issue) who investigate the modern processes involved
with the transport and deposition of soil organic matter during wet
and dry storms on the Têt inner shelf of the northwest Mediterranean
Sea to show that these events act as a bypass corridor for delivery of
land-derived organic matter to the seafloor.
Next, Gennari et al. (2009-this issue) present the results of their
high resolution study of the geochemical signatures of the Holocene
215
sapropel S1. They identify fluctuations in major and minor chemical
element distributions that reveal high-frequency cyclicities that
correspond to millennial and centennial-scale solar cycles. This
correspondence suggests that sapropel deposition is ultimately linked
to global processes, despite being confined to the Mediterranean
basin.
Capozzi and Negri (2009-this issue) investigate the role of sea-
level forced sedimentary processes and their impact on distribution of
the Late Quaternary sapropels in the Mediterranean Sea. They
examine published data on the occurrence of the complete succession
of the S1-S5 sapropels and then focus on two stratigraphic sequences
in the central Adriatic shelf and Middle Adriatic Depression. They find
that sapropels S5 and S1 occur during periods of sea level rise
recorded by the Transgressive System Tracts (Marine Isotopic Stage,
MIS, 5 and 1 respectively). In contrast, sapropels S4 and S3 were
deposited during the Highstand System Tracts that developed
throughout MIS 5 during the late Pleistocene sequence 1. Sapropel
S2 deposition, however, occurred during the warm MIS 3.3 and
follows the MIS 4 sea level drop when an enhanced sediment supply is
recorded during the late highstand and the falling sea level stage of
sequence 1. They also consider the possible influence of sea level
lowering on Mediterranean deep water formation and conclude that
although favourable conditions could be triggered by sea level
oscillation, greater productivity is likely the main cause of the
sedimentation of sapropels.
Morigi (2009-this issue) reconstructs the environmental changes
in the Eastern Mediterranean Sea during sapropel S5 deposition by
means of a high resolution benthic foraminiferal analysis in multiple
216
sediment cores. The study documents that at relatively shallow depths
in the bathyal environment the sea-floor was partially ventilated and
that re-oxygenation had considerably increased during the late phase
of S5 deposition. However, at deeper locations benthic abundance and
diversity strongly decrease during sapropel S5, and microfauna even
disappear in some levels, suggesting the establishment and main-
tenance of stagnant and anoxic conditions at the sea floor until the
end of S5 deposition. In the deepest part of the basin, gradual
repopulation of the benthic foraminiferal community at the top of the
S5 layer indicates a relatively slow bottom re-oxygenation. In the
southernmost site, the benthic foraminifera assemblage records a
short oxygenation pulse during the S5 deposition that is linked to a
short cold spell. Results show that the evolution of the dysoxic–anoxic
conditions as well as the re-oxygenation pattern at the end of the
stagnant period was strongly dependent on the basin morphology.
Schwark et al. (2009-this issue) develop a depositional model for
the Eocene “Pesciara di Bolca” Konservat-Lagerstätte based on
sedimentological, palaeocological, and detailed organic geochemical
data. Their data indicate that the sequence was deposited in the
stagnant bottom waters of a lagoonal-like basin located on an extended
carbonate platform that was sheltered from open marine waters by a
submarine threshold. The high abundance of highly branched
isoprenoids in extractable bitumens suggests that run-off from nearby
land areas provided nutrients to support an algal community
dominated by diatoms. Plant macrofossils, amber, spores and pollen,
and also lipid compositions indicate notable input of land plant organic
matter to the lagoon. The redox regime in general was strongly
reducing, as evidenced by the high concentration of sulfur vs. organic
carbon and excellent kerogen preservation. Molecular indices suggest
a highly stratified water column with anoxic saline bottom water and
fresher surface waters, and traces of derivatives of isorenieratane, the
green sulfur bacteria molecular marker, indicate euxinic conditions
existed at times in the photic zone. The authors conclude that the
depositional setting was comparable to the Solnhofen limestones, but
without the high salinities postulated for the latter.
Moving into the Mesozoic, März et al. (2009-this issue) investigate
black shales from the Coniacian-Santonian OAE3 at two locations in
different palaeo-water depths on the Demerara Rise off Surinam to
identify systematic variations in marine and detrital sediment contribu-
tion, depositional processes, and bottom water redox. Using a wide
range of redox proxies, including Fe/S, P/Al, C/P, and redox-sensitive
trace metals, and P speciation, electron microscopy, X-ray diffraction,
they conclude that anoxic to sulfidic bottom water and sediment
conditions existed throughout the deposition of the black shales. These
extreme redox conditions were periodically punctuated by short-
termed periods with less reducing bottom waters irrespective of
palaeo-water depth. Due to strong similarities of the studied sections
with the stratigraphically older OAE2 black shale on the Demerara Rise,
the authors suggest that the primary mechanisms controlling con-
tinental supply and ocean redox were time-invariant and kept the
western equatorial Atlantic margin widely anoxic over millions of years.
Hetzel et al. (2009-this issue) reconstruct the dynamics of deep
ocean redox palaeoconditions during deposition of Cenomanian-
Turonian OAE2 black shales on the Demerara Rise. Focusing on sulfur–
carbon–metal relationships and especially distribution patterns of iron
and sulfur speciation, sulfur isotope partitioning, and enrichments of
redox-sensitive and sulfide forming trace metals, they identify euxinic
conditions with at least temporarily free hydrogen sulfide in the water
column, similar to the modern deep Black Sea. A change to reducing but
non-sulfidic conditions to allow reductive Fe and Co mobilization in
oxygen-depleted nearshore sediments is inferred from elevated Fe/Al
and Co/Al ratios. Extremely low Mn/Al ratios further support the
existence of an extended coastal upwelling oxygen-minimum-zone off
tropical South America. Finally, the authors discuss a change in the trace
metal inventory of seawater. They postulate the enlargement of euxinic
depositional areas at the global onset of OAE2 that would have led to a
Preface
drawdown of the seawater trace metal reservoir, based on the general
observation that hypoxic to euxinic environments form a sink for trace
metals (e.g., Brumsack, 2006).
Hofmann et al. (2008, 2009-this issue) address aspects of climate–
ocean coupling off northwest Africa during the Lower Albian OAE1b.
They present high resolution records of organic and inorganic
geochemical proxies from DSDP Site 545 on the Mazagan Plateau
that document a complex and rapid environmental change for
onshore continental climate and the offshore upwelling system
associated with OAE1b. TEX86-based SST estimates reveal an abrupt
rise of ~3 °C concurrent with a more than two-fold increase in ac-
cumulation rates for organic-carbon and siliciclastic sediment
components, with an influx of overall finer grained sediment as
inferred from Si/Al and Zr/Al ratios. This new set of data supports the
conclusion that warming associated with OAE1b resulted in an
attenuation of the NE trade wind system over central Africa and a
weakening of local upwelling conditions off NW Africa. The authors
invoke higher continental runoff that may have supplied excess
nutrients to the eastern North Atlantic that in turn fostered greater
production of organic matter and finally led to black shale deposition.
Mutterlose et al. (2009-this issue) analyze the macrofaunal content
and bulk geochemistry (δ13C, δ18O) of the expanded organic-carbon-
rich mudstone sequence of Barremian—early Aptian age exposed in
northern Germany, including the mid early Aptian “Fischschiefer”
equivalent of the OAE1a. They find that the sequence of finely
laminated black shales (“Blätterton”) with organic carbon contents as
high as 7% is interbedded with dark and carbonate-poor clays on a
decimeter to several meter scale that record repetitive fluctuations of
salinity driven stratification of the water column in relation to more
humid conditions in the hinterland. A distinctive positive δ13C
excursion of ~4‰ preserved in belemnite guards is found to correlate
with the global positive δ13C excursion of mid-early Aptian age
following the OAE1a, providing the first record of the positive carbon
excursion for the Boreal Realm. A concomitant shift in δ18O of about
2‰ is interpreted as a distinct SST decrease of ~ 8 °C, a trend that is also
reflected by changes in lithology and organic carbon burial from the
thick early Barremian Hauptblätterton to thin laminites in the late
Barremian. The observations from this study suggest a direct
temperature control on peak anoxic conditions followed by repetitive
and short termed redox fluctuations.
Mailliot et al. (2009-this issue) present records of calcareous
nannofossil and benthic foraminifer assemblages and geochemistry of
two sections from the partly enclosed Causses Basin of the epiconti-
nental shelf of northwest Tethys to infer a progressive environmental
deterioration passing from the Late Pliensbachian to the Early Toarcian.
The data show that the palaeoenvironmental deterioration culminated
during the Early Toarcian OAE with a drastic decrease in nannoplank-
ton production and a temporary disappearance of benthic foramini-
fers, the latter likely in response to bottom water anoxia.
The Palaeozoic unit starts with a contribution from Bond and Wignall
(2008, 2009-this issue), who globally revisit the Frasnian-Famennian (Late
Devonian) mass extinction, comparing new sections in the USA and Europe
(France, Germany, Poland) with published data from locations in Canada,
Australia and China. Several high-frequency relative sea-level changes are
common to the multiple sites, supporting a transgression-anoxia-extinction
link for the late Frasnian to earliest Famennian interval.
Two papers deal with Upper Ordovician-Silurian sediments from
the North African margin of Gondwana. Armstrong et al. (2009-this
issue) examine Upper Ordovician-Silurian black shales of Jordan. They
provide evidence for a consistent increase in photic zone primary
productivity during ice melting and conclude that increased flux of
sinking organic matter led to euxinia extending from the photic zone
to the sediment water interface as evidenced by the widespread
presence of isorenieratane derivatives, which resulted in improved
organic matter preservation. Vecoli et al. (2009-this issue) integrate a
palynological and palynofacies analysis with organic carbon isotope
 Preface
measurements in southern Tunisia. The earliest Wenlock (“Ireviken
Event”) and late Ludlow (“Lau Event”) isotopic excursions are
documented for the first time in high-latitude Gondwana, corroborat-
ing the hypothesis that these excursions reflect global changes in the
oceanic system. Both isotopic excursions are interpreted within a wide
palaeogeographic scenario. The authors propose an extended period
of black shale deposition from Rhuddanian to early Wenlock times
over the North African Gondwanan margin, associated with a coastal
upwelling-promoted productivity increase and a decrease in diversity
of the marine microplanktonic communities.
In the final paper on Palaeozoic palaeoceanography, Challands et al.
(2009-this issue) discuss the origin of grey-black shale cycles within
the Upper Ordovician (Upper Katian) succession of the Welsh Basin.
Using a multi-proxy approach, they document high photic zone
productivity comparable to that of modern coastal upwelling systems
and persistent dysoxic to anoxic conditions in the water column,
interpreting these deposits to be the result of a complex interaction of
productivity and preservation.
Acknowledgements
Special thanks are due to Petr Štorch, who started with us on this
adventure but had to drop out because of other demands on his time.
His contributions were important to the success of the EGU session.
We are particularly indebted to those important individuals who
carefully and conscientiously reviewed the manuscripts that we
received for this Special Issue. We acknowledge their excellent
contributions by naming them here:
Alessandro Amorosi, Achim Bechtel, Carlton Brett, Hans-Jürgen
Brumsack, James Casford, Anna M. Cruse, Olaf Dellwig, Elisabetta Erba,
Karl Föllmi, Oliver Friedrich, David Gallego-Torres, Luca Giusberti,
Michael Hermoso, Carmen Huguet, Steve Kershaw, Christopher
Junium, Timothy W. Lyons, Axel Munnecke, Alex Page, Florentin
Paris, Tatsuhiko Sakamoto, Lorenz Schwark, Jan Schwarzbauer, Caro-
line Slomp, Federico Spagnoli, Helen M. Talbot, Ellen Thomas, Steven
Turgeon, Paul Wignall, Jan Zalasiewicz.
Thanks are due to the authors of the individual research papers for
their hard work and for their efforts to meet the generally stringent
time tables we imposed on them.
Finally we thank Femke Wallien, who encouraged us to organize a
third special issue dealing with “black shales”, Jules Snelleman, and
Fred Kop, who together provided us guidance throughout our period
as guest editors.
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 218–227

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Preface

Phanerozoic organic-carbon-rich marine sediments: Overview and future

research challenges
A. Negri a,⁎, A. Ferretti b, T. Wagner c, P.A. Meyers d
a
Dipartimento di Scienze del Mare, Università Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy
b
Dipartimento di Scienze della Terra, Università degli Studi di Modena e Reggio Emilia, Largo S. Eufemia, 41100 Modena, Italy
c
Department of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK
d
Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan, 48109-1005, USA

a r t i c l e i n f o

Article history:
Received 3 October 2008
Accepted 9 October 2008

Keywords:
Anoxic oceans
Organic-carbon-rich marine sediments
Sapropel
Black shale
Cenozoic
Mesozoic
Palaeozoic

“One of the major obsessions of many early workers, to the mid-
1900s, was the application of uniformitarian principles to deposi-
tional models for black shales“ (Arthur and Sageman, 1994).
The purpose of this overview of organic-carbon(OC)-rich marine
sediments is to provide a brief but current summary of the historical
developments, principle concepts, and remaining challenges in inte-
grated sapropel and black shale research. As such, it provides a
substantive introduction to the Special Issue of Palaeogeography,
Palaeoclimatology, Palaeoecology on “Organic Carbon Rich Sediments
through the Phanerozoic: Processes, Progress, and Perspectives”. Given
this focused scope, the overview does not aim to be comprehensive or
complete but to provide a solid setting for the fourteen individual
research papers that constitute this Special Issue and two previous
special issues (Meyers and Negri, 2003; Negri et al., 2006) that cover
research aspects complementary to this one. Like the individual
contributions, this introduction and overview is organized into
Cenozoic, Mesozoic, and Palaeozoic units. The Cenozoic and Palaeozoic
units are deliberately larger than the Mesozoic unit, acknowledging that
much ground on Mesozoic black shale is already covered in the two
previous special issues. Because the Late Cenozoic sapropels of the
Mediterranean Basin have been extensively studied, understanding how
⁎ Corresponding author.
E-mail address: a.negri@univpm.it (A. Negri).
these near-modern analogs of ancient black shales were deposited
provides a good foundation for understanding how the older sequences
may have evolved. In contrast, because far less is generally known about
the black shales of the Palaeozoic than comparable OC-rich sequences of
either the Cenozoic or the Mesozoic, a more comprehensive summary
and comparison of the more ancient sequences is particularly appro-
priate to the theme of this Special Issue.
1. Introduction
Sediments rich in organic carbon are restricted to small areas along
continental margins in the modern ocean and have rarely accumulated
during the Cenozoic, yet organic-rich sediments were widely deposited
during multiple intervals of Mesozoic–Palaeozoic time and even earlier
during the Proterozoic–Archean. Global marine deposits document that
episodes of accumulation of OC-rich sediments occurred in different
regions and at different times. These episodes were linked to climatic
and palaeoceanographic perturbations that resulted in massive fluctua-
tions in hydrologic and nutrient cycles and in ocean chemistry and that
recurred throughout geologic time. However, the paucity of surviving
Palaeozoic and earlier black shale sections makes it difficult to
impossible to recognize the internal structure of global events that are
common in younger OC-rich sedimentary sequences.
As underlined below, the marine sections in many localities consist
of intercalated carbonates and shales that may grade into pure
carbonate or black shale sedimentation, often reflecting shallowing/

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.10.002
 A. Negri et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 218–227
deepening of the depositional environments due to sea-level fluctua-
tions superimposed on longer term orbital climate variability.
Evidence for these past changes occurs at different time scales and in
shallow to deep marine settings across all latitudes. Their temporal and
spatial differences document regional overprinting and amplification
or attenuation of global processes.
In the Late Cenozoic, laminated sections in expanded OC-rich
sequences are sometimes found; they provide down to annual-scale
palaeoclimate histories. Similar expressions of climate and sea-level
variability are observed, although with less conclusive time control,
in the Mesozoic, when “Oceanic Anoxic Events” (OAEs) were
deposited in mid-Cretaceous marine environments that experienced
a series of relatively short periods of rapid change with massive
effects on the global carbon cycle. These short intervals evidently
were associated with anoxic or even sulfidic (euxinic) conditions in
the water column and were accompanied by widespread extinction
events. The same mechanisms, episodes of widespread bottom water
anoxia, have been postulated for Palaeozoic OC-rich sediments that
record the long duration of these conditions and that accompany the
Devonian and Permian extinction events, two of the major crises in
life history.
After more than half a century from the first report of sapropels in
deep sea sediments (Kullenberg, 1952) and more than 30 years after
the basic paper of Schlanger and Jenkyns (1976) defining the OAEs as
global phenomena, the significance of the burial of large amounts of
organic matter in deep-sea sediments on the global carbon cycle and
the nature of the palaeoceanographic and palaeoclimatic conditions
leading to these peculiar deposits remain topics of lively debate. In this
overview to Phanerozoic black shales, we briefly trace the history
of sapropel and black shale studies since the first discovery of these
OC-rich sequences to their modern interpretation, and we highlight
recent achievements and remaining challenges in their research.
2. Cenozoic organic-carbon-rich marine sequences
2.1. Investigations of Miocene–Holocene Mediterranean Sea sapropels
The word “sapropel” is a combination of ancient Greek words sapros
and pelos, meaning “putrefaction” and “mud”, respectively. It is a term
used in marine geology to describe dark-coloured, fine-grained
sediments that are rich in amorphous organic matter. The historical
definition of Mediterranean sapropels by Kidd et al. (1978) describes
them as well-delimited layers within open marine sediments, with
thickness N1 cm and organic carbon content N2%. How such OC-rich
layers were deposited in the oligotrophic Mediterranean Sea has been a
subject of interest since Bradley (1938) first predicted the widespread
occurrence of sapropels in the Mediterranean basins from study of
exposures in southern Italy. He interpreted the sapropels as recording
stagnation episodes during the Quaternary. Later, Kullenberg (1952)
interpreted sapropel formation as resulting from interstitial salinity
variations based on cores obtained by the 1948 Swedish Deep Sea
Expedition. A decade later, Olausson (1961) presented a glacio-eustatic
sea-level change model for sapropel formation that was subsequently
variously reinterpreted by other authors (e.g., Chamley, 1971; Miller,
1972; Ryan, 1972; Nesteroff, 1973; Cita et al., 1973; McCoy, 1974).
However, Olausson's classic glacio-eustatic model gradually became
insufficient to explain all aspects of sapropel formation as more
information about their properties accumulated.
DSDP Leg 42 recovered sapropel layers in cores of Pliocene to
Quaternary sediments at multiple sites in the eastern Mediterranean.
Some of these layers predate the onset of the strong glacial–interglacial
cycles that affect eustatic sea level. Sigl et al. (1978) inferred that since
the sapropels are interbedded as dark layers in more or less normal
light-colored “open marine” sediments, the formation of these layers
records short-lived but catastrophic alterations in oceanographic
conditions that were probably caused by climate changes. They further
219
suggested that differing faunal and lithological characteristics within
sapropelic layers of different ages indicate different mechanisms of
sapropel formation. Brongersma-Sanders (1957) had postulated that
bituminous rocks may be formed when “either the supply of oxygen to
the lower water layers is excessively low (persistent stagnation) or the
supply of dead plankton and other oxidizable material is extremely high
(hypertrophy)”. Sigl et al. (1978) consequently inferred that the dual
mechanisms of greater production and better preservation of organic
matter may help to explain the presence of sapropelic sediments in
“preglacial” lower Pleistocene and upper Pliocene sediments recovered
by DSDP Leg 13 (Ryan et al., 1973; Cita, 1973), as well as in Miocene
sediments recovered by DSDP Leg 42. Moreover, the discovery of
sapropelic sediments in the western Mediterranean (Kidd et al., 1978)
revealed that their deposition was not entirely restricted to the eastern
basin as had been believed until then. Therefore, new explanations for
sapropel formation had to be considered.
Among the various processes that have been invoked to explain
sapropel formation (see Rohling, 1994, and Rohling et al., in press, for
reviews), variations on the classical “stagnation/anoxia” and the
“increased productivity” models remain the most common. According
to the stagnation/anoxia model, anoxic bottom conditions are caused
by a strong stratification of the water column that prevents vertical
mixing and oxygen supply to the bottom waters. In the Mediterra-
nean, the origin of this stratification was explained as owing to
increased Nile river runoff linked to the periodic enhancement of the
East African monsoons (Rossignol-Strick, 1983, 1985) and, later, by
increased rainfall and river discharge along the northern margins of
the eastern Mediterranean Sea (Cramp et al., 1988; Rohling and
Hilgen, 1991). In the “productivity” model, sapropel deposition is
linked to enhanced organic matter flux from highly productive surface
waters (Calvert, 1983; Calvert et al., 1992), inasmuch as the present
production of organic matter in the eastern Mediterranean cannot
account for the high values of total organic carbon (TOC) characteriz-
ing these layers (Calvert, 1983). In support of this view, evidence of a
significant increase of productivity at times of sapropel deposition is
revealed by palaeo-productivity proxies, such as Ba and marine barite
concentrations (e.g., Thomson et al., 1995, 1999; Martinez-Ruiz et al.,
2000, 2003; Gallego-Torres et al., 2007). To help explain the increased
productivity, Sarmiento et al. (1988) and Howell and Thunell (1992)
invoked a radical change from the modern anti-estuarine circulation
to an estuarine circulation in the Mediterranean Sea.
After this first phase of research in which the scientific community
tended to assume that the various causative processes were mutually
exclusive, some authors (Rohling and Gieskes, 1989; Castradori, 1993;
Rohling, 1994; Emeis et al., 1996, 2000) proposed a mechanism resulting
from the combination of the two processes – stratification and
productivity increase – that could have been caused by an increase of
nutrient input via river runoff. However, questions remain regarding the
extent and dynamics of the anoxic/dysoxic layer in the water column.
The low-oxygen zone has been variously described as a near-surface
zone in which oxygen becomes depleted (Sancetta,1999; Meyers, 2006),
a large water mass extending through much of the water column (Murat
and Got, 2000; Stratford et al., 2000), and as an “anoxic blanket” that
exists above the sediment/water interface (Casford et al., 2003).
Another fundamental question has centered on what organisms
were responsible for the increased primary productivity and how they
evolved through time. Are all of the multiple sapropel layers derived
from organic matter made by the same group of primary producers? If
not, how were environmental conditions different from location to
location and through time? Kemp et al. (1999), for example, propose
that diatom mats formed during summer seasons of prolonged
stratification resulting from Nile run-off. These mats sank rapidly at
the beginning of autumn–winter wind mixing and delivered massive
loads of organic material to bottom sediments that quantitatively
consumed the available oxygen in the water column. From mass-
balance calculations, Kemp et al. (1999) argue that all of the organic
220 A. Negri et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 218–227
carbon retained in the sapropels could have been supplied by these
diatoms. Although the mat model seems limited only to those
uncommon sapropels containing diatom frustules, diatom opal is
highly soluble, and therefore sapropels lacking diatom microfossils
may once have contained them. Following this study, Sancetta (1999)
argued that the diatom mechanism proposed might also apply to
other OC-rich laminated strata, such as the 125–85 million-year-old
mid-Cretaceous black shales.
A further multi-process interpretative step is typified by Meyers
(2006), who suggested that increased continental runoff would have
delivered abundant nutrients that would have first stimulated algal
productivity, magnified export of organic matter, and increased mid-
water oxygen demand. The combination of surface water dilution,
which increased salinity stratification of the upper water column and
thereby discouraged mixing and mid-water ventilation, and magni-
fied oxygen draw-down would have intensified and expanded the
oxygen minimum zone (OMZ) such that anoxia intruded into the
photic zone. After photosynthetic nitrogen-fixing bacteria and
chemosynthetic archaea became established, their primary produc-
tivity would have first augmented and then potentially would have
superseded that of the algae (e.g., Kuypers et al., 2001, 2002a,b).
Accordingly the shift to microbe-amplified productivity would have
persisted until climate reverted to less wet conditions that forced a
return to less stratified, less productive and subsequently more
oxygenated conditions in the surface ocean.
Recent approaches to investigate and to explain how sapropels
were formed have evolved towards modeling methods. Studies on
thermohaline circulation suggest that a weakening of the present-day
anti-estuarine circulation in the Mediterranean can lead to the
deposition of enough organic carbon to account for the formation of
the upper Pleistocene–Holocene sapropels S5 to S1 (Myers et al.,
2000; Stratford et al., 2000). Earlier sapropels may have similarly been
deposited. More recently, Bianchi and co-authors (2006) suggested
that modified thermohaline circulation supplying oxygen only to the
upper 500 m of the water column, when coupled with increased
productivity in the photic zone, can cause the development of an
anoxic blanket at the sea-floor. Finally Meijer and Tuenter (2007)
pointed out that the effects of (1) increased discharge of northern
borderland rivers and (2) an increase in net precipitation over the sea
itself are of equal or even greater importance than an increase in Nile
discharge in diminishing ventilation of deep waters.
Deep-sea and outcrop sequences reveal that sapropels occur
cyclically, strongly suggesting that they are related to the “Milankovitch
cycles” linked to the Earth's orbital cycles of eccentricity (100–400 ky),
obliquity (41 ky) and precession (19–22 ky). Correlation of the cyclic
occurrence of sapropels in the Mediterranean to the orbital variations
was achieved by Hilgen (1991a,b) and later refined by Hilgen et al.
(1995), who developed a continuous record of sapropel occurrences as
far back as the Late Miocene and correlated each sapropel to a well
defined precession cycle. Because these orbital variations determine the
global, seasonal and latitudinal distribution of solar insolation, they
result in repetitive climatic fluctuations. As shown by Hilgen et al.
(1995), sapropel deposition occurred during precession minima, when
the northern hemisphere received maximum summer insolation and
climate in the Mediterranean region was relatively wet.
The correlation of sapropel occurrences to orbital frequencies has
great value to chronology because cyclo-stratigraphy in combination
with other information, such as biostratigraphy and other sedimento-
logical features, allows accurate age determinations, better estimates of
sedimentation rates of individual sapropels, and comparison of same-
age sapropel layers in different settings. These features are ultimately
based on the orbital occurrence and the isochrony of each layer.
Recognition that the sapropel record is sensitive to post depositional
oxidation has been growing. In recent times, a number of investigators
have pointed out the potential of in situ oxidation in biasing the record of
sapropels. Sapropels can evidently experience variable amounts of top-
down oxidation after their deposition such that they rarely maintain their
original thicknesses and compositional features (e.g., Löwemark et al.,
2006; Larrasoaña et al., 2006; Thomson et al., 2006). One implication of
this phenomenon is that the original thickness and TOC concentration of
a specific sapropel layer can influence the rate and degree of post
depositional oxidation. Another is that the sub-surface burial depth and
the position of the depositional setting with respect to deep water
circulation can both play major roles in the preservation of sapropels.
Consequently, recognition of this phenomenon cautions against over-
interpretation of sapropel presence or absence and over-dependence on
them as geochronological tools. For example, post-depositional erasure of
a weakly developed sapropel layer could badly skew an orbitally based
timescale that does not take this possibility into consideration.
A particularly interesting and important finding of OC-rich layers in
the western Mediterranean illustrates another potential problem with
over-dependence on sapropels as geochronological markers and at the
same time illuminates how OC-rich sediments can be deposited.
Rogerson et al. (2008) describe OC-rich layers in post-glacial sediments
of the Alboran Basin that could be confused with the widely expressed
Holocene S1 sapropel. However, they demonstrate that the onset of the
OC-rich layers predates the S1 sapropel by some 4–5 ky. They conclude
that deposition of the Alboran Sea OC-rich layers was the result of a strong
reduction in surface water density and a shoaling of the interface between
the intermediate and deep waters during the latest deglacial period.
Hence, the palaeoceanographic changes associated with OC-rich layers
were much like those that are believed to have accompanied deposition of
most of the sapropels in the greater Mediterranean Sea, but they were
related to local processes in the Alboran Sea and not to precessional cycles.
2.2. Other Cenozoic OC-rich sediments
Although the Mediterranean sapropels are the most studied OC-rich
Cenozoic sequences that are associated with low-oxygen depositional
settings, similar sequences have been deposited in other semi-enclosed
basins during this Era. Some examples are the Holocene Black Sea (Aksu
et al., 1995; Giunta et al., 2007), the early Holocene Marmara Sea (Kirci-
Elmas et al., 2008), and the late-glacial Japan Sea (Tada et al., 1992; Khim
et al., 2007). In addition, modern organic carbon-rich sediments are
being deposited in unusual low-oxygen environments such as Medi-
terranean anoxic brine-filled basins (cf. Cita, 1991; Negri, 1996), and in
silled near-shore basins such as the Santa Barbara Basin and the Cariaco
Basin. Some of these locations are considered as modern or near-
modern analogs of the older depositional settings that favoured
improved preservation of organic matter and led to accumulations of
sapropels and black shales.
OC-rich sediments have also accumulated in Cenozoic settings that
have not been low in oxygen. The best examples of such places are the
large upwelling systems on the eastern margins of the modern-day
Atlantic and Pacific oceans, where high rates of marine productivity are
sustained by strong vertical mixing of the surface ocean. The high
production of organic matter associated with eastern margin upwelling
in the Atlantic started ca 7 Mya in the Late Miocene (Diester-Haass et al.,
2002). An earlier onset of high productivity along the eastern margin of
the Pacific is recorded by the Monterey Formation, which consists of
laminated sediment enriched in organic carbon that was deposited
during the Serravallian–Tortonian (14–7 Mya) Monterey event
(Vincent and Berger, 1985). Subsequent study of the Monterey
Formation has revealed that preservation of organic carbon is linked
both to orbital-scale climate changes and to regional conditions during
the Middle to Late Miocene (John et al., 2002). Other examples of studies
into how OC-rich sediments accumulate under areas of high productivity
include the Late Quaternary off northern Mexico (Ganeshram et al.,1999),
the California Margin (last 60 ky; Dean, 2007). Finally, OC-rich sediments
are known to accumulate in the Norwegian Greenland Sea, even if here
organic matter has a residual origin being mainly derived from fossil
reworked organic matter (last 60 ky; Wagner and Hölemann, 1995).
 A. Negri et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 218–227
Table 1
A summary of the mid-Cretaceous Oceanic Anoxic Events (OAEs). Approximate
absolute-age durations are from Ogg et al. (2004) and Wagner et al. (2004)
Event Common name Geologic time Absolute duration
OAE 3 (none) Coniacian–Santonian 87.3–84.6
OAE 2 Bonarelli Event Latest Cenomanian 93.8–93.5
OAE 1d Breistroffer Event Late Albian 100.6–100.2
OAE 1c Tollebuc Event Late Albian 103.7–103.4
OAE 1b series of sub-OAEs
Urbino Event Early Albian 110.9–110.6
Paquier Event Early Albian 112.0–111.6
Jacob Event Late Aptian 113.6–113.2
OAE 1a Selli Event Early Aptian 124.2–123.4
Episodes of regionally confined accumulations of OC-rich sediments
also occurred earlier in the Cenozoic. Intervals of “black shales” have
been recovered in Arctic sediments (Stein, 2007), the Tethyian margin in
the North between the Crimea and Uzbekistan (Gavrilov et al., 1997) and
the South in Egypt and Israel (Speijer and Wagner, 2002) that are related
to the 6 My Paleocene–Eocene Thermal Maximum period of global
warming (Zachos et al., 2008). Off equatorial West Africa porcellanites
with enhanced organic carbon concentrations and good hydrocarbon
potential were deposited during the Middle to Late Eocene (Wagner,
2002). Interesting shallow water Eocene laminated sediments exist in
Tunisia (Henchiri, 2007). Sometimes these events are not fully
developed (i.e., Eocene–Oligocene; Coccioni and Galeotti, 2003).
Rhythmically bedded sediments occur in the Oligocene–Miocene
sediments of the Paratethys that are postulated to be an earlier analog
of the modern Black Sea (i.e., Kruge et al., 1996; Schulz et al., 2005).
3. Mesozoic organic-carbon-rich marine sequences
Extensive sequences of marine black shales containing 2 to 30%
organic carbon were episodically deposited from 183 My to 83 My
(Toarcian through Santonian ages) during the Mesozoic Era. Continuing
investigations of the nature of the marine black shales and the processes
leading to their formation have placed black shale research into the
centre of today's debate on global warming and climate change. The
foundations for the current focus on extreme warm climate, rapid
biogeochemical cycling and associated climate/environmental change
were established half a century ago when petroleum industries jointly
developed the first integrated concepts to assess and predict general
environmental boundary conditions and preferential depositional
settings for oil-prone source rocks (e.g. the “Organic Facies” concept
summarized by Jones, 1987). In parallel the rise of isotope and organic
geochemistry enabled academia to postulate the fundamental concept
of the “Oceanic Anoxic Events”, or OAEs (Schlanger and Jenkyns, 1976)
that are listed in Table 1. Both basic concepts have not lost attraction over
time. Indeed, they have been merged with other critical aspects of Earth
and Life Science and have substantially evolved into what is today a truly
cross-disciplinary strategy to understand and quantify key elements of
the Earth's climate system and how it interacts with the global carbon
cycle.
Current research into the mid-Cretaceous OAEs serves as a focal
point for research into extreme climate in a broader sense. Together
with detailed investigation into the Late Paleocene Thermal Maximum
(e.g., Speijer and Wagner, 2002; Zachos et al., 2005; Higgins and
Schrag, 2006; Zachos et al., 2006; Schouten et al., 2007; Smith et al.,
2007) and, although less well publicized, into OAE equivalents from
the Jurassic (Hesselbo et al., 2000; Kemp et al., 2005; Cohen et al.,
2007; Hesselbo et al., 2007; Pearce et al., 2008), the Miocene
(Woodruff and Savin, 1991; Raymo, 1994; Pagani et al., 1999; Föllmi
et al., 2005; Holbourn et al., 2007; Vincent and Berger, 1985), and the
Plio–Pleistocene (see recent summary by Meyers, 2006), Cretaceous
black shale research today addresses a wide range of questions that
221
partly emerged from the original concepts. Taking particular advan-
tage of the spectacular analytical progress in organic and isotope
geochemistry and computer simulations over the last decade, the new
challenges are beyond traditional discussions of OAEs. They include
Ma (∼2.7 My) but are not limited to the short term dynamics of the climate system in
Ma (∼300 ky) a generally warmer world, processes and phase relationships con-
Ma (∼400 ky
necting the atmosphere with the surface ocean (Dumitrescu et al.,
Ma (∼300 ky)
2006; Forster et al., 2007; Wagner et al., 2008), orbital forcings
(Beckmann et al., 2005; Gale et al., 2005; Sageman et al., 2006;
Ma (∼300 ky) Mitchell et al., 2008), regional effects on global processes, in particular
Ma (∼400 ky) the role of land–ocean interactions in driving ocean redox and shallow
Ma (∼400 ky)
Ma (∼800 ky)
ocean circulation (Nederbragt et al., 2004; Wagner et al., 2004; Mort
et al., 2007), nano-scale organo-mineral relationships (Kennedy et al.,
2002), redox variability and its impact on element and nutrient
cycling (Crusius et al., 1996; Pearce et al., 2008; Jenkyns et al., 2007;
März et al., 2008), the role of microbial life in sustaining conditions
favouring formation of black shale and utilizing carbon from them
under modern conditions (deep biosphere) (Krumholz et al., 1997;
Coolen et al., 2002; D'Hondt et al., 2004; Arndt et al., 2007), triggers,
thresholds and time scales for punctuated climate perturbations
involving the emplacement of large igneous provinces (Sen et al.,
2006, Kuroda et al., 2007; Turgeon and Creaser, 2008)and biotic
responses (Larson and Erba, 1999; Leckie et al., 2002), methane
outbursts (see review in Jenkyns, 2003; Kemp et al., 2005), wide-
spread but short term polar glaciation (Bornemann et al., 2008), and
finally high-quality sedimentary climate records linked with biogeo-
chemical and global climate models (Bice et al., 2006; Flögel and
Wagner, 2006; Wagner et al., 2007), also allowing projections into the
future (Flögel et al., 2008). In sum, these challenges address questions
of global relevance where progress is still to be made. Progress often is
hampered by the lack of basic constraints, including accurate chro-
nology, knowledge of sedimentary parameters, and – importantly –
the lack of continuous expanded sediment sections necessary to
extract sub-Milankovitch scale (centennial–millennial) climate change
in the past. Despite gaps, recent achievements like those presented in
this Special Issue show various promising avenues where Cretaceous
black shale research in its wider sense is heading.
4. Palaeozoic organic carbon rich sequences
4.1. A global view
The Palaeozoic, spanning from 542 to 251 My, covers a period of
about 290 My, exceeding the combined duration of the Mesozoic and
Cenozoic eras. This long time interval has been characterized by a
variety of environmental and palaeogeographic settings, for which
any generalization is often too restrictive. Nevertheless, most of the
Palaeozoic from the Cambrian to the Carboniferous, has been com-
monly regarded as a global greenhouse period (Berner, 1994; Berner
and Kothavala, 2001), interrupted by major but short-lived ice ages in
the Hirnantian (Late Ordovician), in the Late Devonian and in the Early
Carboniferous (Achab and Paris, 2007).
The whole Palaeozoic is punctuated by a profusion of episodes of
black shale deposition that represent a common and not unusual
sediment for that time. Sections in many localities consist of intercalated
carbonates and shales that may grade into pure carbonate or black shale
sedimentation, often and simply reflecting shallowing/deepening of the
depositional environment due to sea-level fluctuations. Most of the
attention that has so far been given to OC-rich deposits in the Palaeozoic
has mostly reflected economic interests in hydrocarbons and metals.
Only recently a pure geochemical approach, including the application of
the three broad categories of biomarkers, carbon isotopes and elemental
compositions, has been attempted in order to understand the genesis
and significance of these peculiar deposits.
According to Nowak (2007), “black shales are most often described as
argillaceous, argillaceous–pelitic, argillaceous–siliceous and argillaceous–
222 A. Negri et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 218–227
carbonate sediments with higher amounts of more or less transformed
organic matter responsible for the black or dark grey colour of these
sediments.” The abundance of organic matter does not, per se, imply black
shales. The Palaeozoic, in fact, is also characterized by fossiliferous OC-rich
limestones (e.g. the Silurian–Devonian Orthoceras limestones bordering
northern Gondwana), known for their black colour and whose high
organic content is revealed by a peculiar bituminous smell and by the
common inclusion of soft hydrocarbon nuclei.
Going ever deeper into the past, two factors keep playing a more
and more fundamental role: preservation and time resolution. OC rich
sediments, either in form of black shales or limestones, do not
necessarily reflect periods of elevated deposition of high organic
matter but may paradoxically simply represent times of better organic
matter preservation. In this perspective, at least, a simple measure of
the total organic content of the sample appears insufficient to define
high deposition of organic matter. Then, even well-dated sequences
do not offer the high-resolution records needed to fully document or
delineate short-time processes. Within these limitations, at least three
major black-shale depositional events appear to have particularly
attracted the attention of Palaeozoic specialists.
4.2. Carboniferous–Permian
In the Early Carboniferous, many large continents were concen-
trated in the southern hemisphere, where an ice cap had covered the
South Pole. The oceans between Euroamerica and Gondwana began to
close and, by the end of the period, the western half of Pangea was
already assembled. During the Permian, other major land masses
collided with the final assembly of the single Supercontinent of
Pangea, spreading over the equator with a pole to pole distribution. A
new ocean was rapidly growing on its southern end, the Tethys, ready
to assume a dominant role in the Mesozoic.
Two well-known OC-rich sediments developed in the Late Palaeozoic
of Central Europe, respectively in the Late Carboniferous–Early Permian
and in the Late Permian, the latter known as Kupferschiefer (TOC up to
20%) and famous for the richness in copper and silver. A recent
petrographic study of the organic matter preserved in these levels
from SW Poland (Nowak, 2007) associates the older shales to an open-
lacustrine depositional environment with organic matter mostly of
sapropelic origin. A peculiar distinct lamination of microscopic algal-rich
laminae intercalated with thicker clay-rich laminae clearly indicates a
seasonal deposition. The Late Permian OC rich sediments, having
bituminite as major organic component, indicate deposition in a shallow
marine depositional environment with very small terrestrial input
(Nowak, 2007).
Herbert and Compton (2007) recently confirmed deposition in a
glacio-lacustrine environment for lower Permian sediments of the
Karoo Basin of South Africa, including black shale units and documenting
transition from full glacial to non-glacial conditions. High surface-water
productivity associated with these OC rich shales had been deduced by
Faure and Cole (1999) in all southwestern Gondwana basins. Piper and
Perkins (2004) applied a depositional model, established from trace-
element accumulation rates in the Cariaco Basin, to the Permian
Phosphoria Formation of northwest United States in order to unravel
the palaeoceanography of its deposition. The investigated Permian unit is
represented by a black phosphate deposit containing up to 15% organic
carbon and deposited under conditions of O2 depletion. The study of
Piper and Perkins (2004) led to recognition that the hydrography of the
Permian Phosphoria Basin corresponds to modern upwelling environ-
ments, with a moderate primary productivity.
4.3. Devonian
In the Devonian, many of the Early Palaeozoic oceans were closing.
Laurasia and Baltica collided, forming Laurussia, while the southern
continents remained tied together in the supercontinent of Gondwana.
The Devonian was a time of widespread formation of black shales.
Among these, Late Devonian OC-rich sediments have attracted special
consideration as they coincide with mass-extinction pulses and global
signals of marine anoxia. Two distinct black OC-rich horizons (Kellwas-
ser horizons) characterize Late Frasnian sequences of Central Europe and
North Africa and have recently been documented also in the United
States (e.g., Bond and Wignall, 2005; de la Rue et al., 2007). Lower
Frasnian black shales, with TOC up to 14%, deposited diachronously in
several North African areas and also in Europe (Lüning et al., 2004), and
were associated with an anoxic phase (Frasnes event) preceding the
Kellwasser events. In deeper basinal-settings, anoxic sediments rich in
organic matter persisted for longer periods till the earliest Famennian
(Joachimski et al., 2001; Bond et al., 2004). Another global event, the
Hangenberg event, occurred in the latest Devonian in association with
the second strong pulse of the Devonian extinction.
Several studies have dealt with these deposits reflecting, again, the
usual dilemma between the two end-member factors: “preservation”
versus “productivity” models. de la Rue et al. (2007) recently approached
the Frasnian/Famennian boundary with a multiproxy study (by the use of
chemical, sedimentological and biotic proxies) of the New Albany Shale, in
Indiana, documenting a drastic change from acritarch- to prasinophyte-
dominated associations across the F/F boundary, indicating basinal
deeper-water settings receiving a continuous input of in situ marine-
derived organic matter in anoxic conditions. Bond et al. (2004) referred the
Kellwasser events, studied in a broad range of European occurrences, to
intense and widespread marine anoxia. In particular, the upper episode
was interpreted as “an epicontinental seaway phenomenon, caused by the
upward expansion of anoxia from deep basinal locales rather than an
“oceanic” anoxic event that has spilled laterally into epicontinental
settings.” The same anoxic event appears to have been the only of the two
Kellwasser episodes to be synchronous either across Europe (Bond et al.,
2004) or the western United States (Bond and Wignall, 2005).
Joachimski et al. (2001) analyzed geochemically the Kellwasser
horizons in Poland, there developed in carbonate sequences domi-
nated by cephalopod limestones (TOC up to 4.9%), owing to tropical to
subtropical palaeolatitudes (Marynowski et al., 2000). According to
Joachimski et al. (2001), the short term transgressive–regressive
pulses identified at a global scale by Johnson et al. (1985) caused the
spread of anoxic water in formerly well-aerated environments (with
episodic euxinic conditions into the photic zone) and intensified
continental runoff, with consequent higher supply of continent-
derived nutrients and increase in primary productivity. Evidences of
photic zone euxinia and wildfires have been recently documented in
Poland from a black shale horizon equivalent to the Hangenberg
global event (Marynowski and Filipiak, 2007).
Buggisch et al. (2008) recently related three latest Devonian to
earliest Pennsylvanian positive excursions in δ13C, paralleled by the
deposition of black shales in central, northwest and southern Europe,
to concordant shifts in δ18Oapatite interpreted as signals of climatic
cooling and ice accumulation at high latitudes.
4.4. Ordovician
The Ordovician was a period of intense plate dispersion with land
masses mostly concentrated in the southern hemisphere and a vast
oceanic area occupying the northern half of the globe. The different grade
of dispersion of the palaeoplates produced a diverse degree of
endemicity among marine biota. In addition, the new land-mass
configuration led to the establishment of an active thermohaline oceanic
circulation by the Middle–Late Ordovician resulting in an effective
mixing of the pelagic elements and in an intense upwelling able to
amplify phytoplankton production (Achab and Paris, 2007). By the end of
the period, Gondwana regions were located at high latitudes in cold
climates during the onset of a severe glaciation with the rapid build-up of
a huge ice-cap. Other areas occupied tropical and subtropical latitudes,
with carbonate deposits dominating in Baltica and, partially, in Laurentia.
 A. Negri et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 218–227
The glaciation at the end of the Ordovician has attracted interest not
only for its association with a major extinction event, but also because it
required unusual causes due to its short duration (approximately 1 My)
during an otherwise warm period in Earth's climate, characterized by an
atmospheric CO2 concentration that was 15–20 times its present level
(Page et al., 2006). Several other minor glacial episodes appear to have
been associated, and Page et al. (2006, 2007) recently referred to a glacial
Early Palaeozoic Icehouse (Late Ordovician–early Silurian), marked by
seven glacial maxima, intercalated by brief intervals of glacial ameliora-
tions. OC-rich black shales containing up to 10% TOC were deposited
extensively especially along the northern Gondwana shelf during the
same time interval (e.g., Lüning et al., 2000; Armstrong et al., 2005; Le
Heron et al., 2008). The short duration of the glaciation was explained by
a rapid drawdown of atmospheric CO2 below a critical glacial inception
threshold triggered by an amplification in marine productivity and
consequent organic carbon burial (Brenchley et al., 1994, 1995). The
increased phytoplankton production eventually led to the replacement
of greenhouse by icehouse conditions (Achab and Paris, 2007). A similar
approach was advanced by Page et al. (2006), who interpreted the
deposition of graptolitic black shales as a negative feedback mechanism
responsible for drawing down CO2 and preventing runaway melting in a
peculiar climatic situation in which elevated atmospheric CO2 prohibited
carbonate formation.
Armstrong et al. (2005, 2006) discussed and compared the
upwelling and the silled basin models (either the elevated productiv-
ity or the enhanced preservation model) in order to interpret the
deposition of Late Ordovician deglacial organic-rich black shales from
Jordan. They favoured the “expanding puddle model” of Wignall
(1994), suggesting that anoxic conditions were maintained for
thousands of years due to a pronounced salinity stratification with a
surface layer of fresher water derived by ice-melting. An intensified
bioproductivity was sustained by continuous supply of meltwater-
derived nutrients in the mixolimnion. With the onset of the deglacial
transgression, black shales extended to marginal areas.
A different view had been proposed by Lüning et al. (2000), and
discussed in Lüning et al. (2006), who favoured the basal transgressive
black shale model for earliest Silurian oil shales from Arabia and North
Africa, source of 80–90% Palaeozoic hydrocarbons of North Africa and
with up to 17% total organic content (Boote et al., 1998). They
assembled a huge quantity of information, including unpublished
petroleum exploration well data, and suggested that the melting of
the Late Ordovician ice-cap produced a very rapid transgression in a
strongly irregular palaeorelief. An almost instantaneous anoxic event
was induced by a favourable combination of several factors in the
Rhuddanian, persisting just 1–2 My and resulting in the excep-
tional preservation of the laterally discontinuous northern Gondwana
OC-rich basal Silurian shales.
4.5. Palaeozoic organic matter producers
The Palaeozoic marks an interval of extraordinary and unparalleled
achievements in the history of life. In the Early Palaeozoic, life existed
in a solely marine scenario. By the Silurian, a dramatic innovative event
was quickly occurring, with terrestrial environments that were subject
to the rapid colonization and diversification of land plants. From then
on, land plants strongly became able to modify the global carbon cycle
and consequently the climatic history of the Earth, removing CO2 from
the atmosphere and resulting in a significant and persistent storage of
CO2 starting in the Devonian (Peters-Kottig et al., 2006). Even within
terrestrial floras, significant revolutions occurred in the Palaeozoic.
Edwards (1998) recognized four major evolutionary steps in Palaeozoic
land plant evolution. Ordovician and Silurian vegetation is represented
mainly by spores while tracheophytes (or vascular plants) began to
radiate in the Late Silurian–Early Devonian. Seed-plants appeared in the
Late Devonian and, by the Permian, gymnosperms became dominant.
Berner (1998), by the use of GEOCARB II applied to the whole
223
Phanerozoic, revealed that the rise of vascular plants in the Palaeozoic
“had one of the most dramatic effects on CO2 of any process occurring
within the past 550 Ma.” Important drops in CO2 occurred in the
Devonian, due to intensive weathering of silicate rocks by deeply rooted
plants, and in the Carboniferous and Permian, due to enhanced burial of
organic matter resulting probably from production of microbially
resistant plant remains such as lignin. By the Late Palaeozoic, either
marine or terrestrial organisms were able to contribute to organic-rich
sediments. At the end of the Permian, the most severe mass extinction of
the life-history took place and a completely different life-scenario was
opened.
In this context, which were the major producers of Palaeozoic organic
matter? Schwark and Empt (2006) investigated sterane compositions in
Late Ordovician to Late Permian rock samples in order to unravel the
evolution and diversification of Palaeozoic phytoplankton (mainly
represented by Cyanophytes, acritarchs and algae) and to recognize
any signal recorded by algae that might document causes/effects of the
extinction events. Their data revealed a stepwise but persistent increase
in C28/C29-sterane ratio caused by a drastic change in the community
structure of green algae at the Devonian/Carboniferous boundary and
contemporary to a great decline of acritarchs. More primitive C29 sterane
producing algae were in fact replaced by modern C28-sterane-producing
algae. This event has the same fundamental significance as more recent
floral revolutions like the appearance of haptophyte algae or diatoms
(Schwark and Empt, 2006). A “phytoplankton blackout” resulting also
from a massive drop of acritarchs at the Devonian/Carboniferous
boundary developed between the Early Carboniferous and the Late
Triassic. A similar gap was not reported among benthic invertebrates. The
strong and persistent increase in the C28/C29-sterane ratio signal
occurring at the Devonian/Carboniferous could reveal the appearance
of a non encysting, hardly fossilizing algal group, as earlier suggested by
Strothers (1996).
In the marine realm, graptolites also made an important contribu-
tion. Organic matter preserved in lower Silurian black shales from the
Barrandian (Czech Republic) consists primarily of graptolites and
subordinate chitinozoans (Suchý et al., 2002).
The study of terrestrial organic matter has recently attracted interest
as a more detailed knowledge of terrestrial organic matter allows a
correlation between terrestrial and oceanic realms, in order to determine
if oceanic carbon perturbations are purely oceanographic in their extent
or if they have affected the entire ocean–atmosphere system. Aromatic
hydrocarbon biomarker analysis was performed on organic matter of
terrestrial origin from Middle Devonian to Late Permian coal basins of the
Euramerian flora realm (Armstroff et al., 2006), mostly consisting of a
mixture of type II–III kerogen with TOC up to 81.5%. According to
palynological and palaeobotanical studies on Late Carboniferous Eur-
american coal basins (Auras et al., 2006), a major change in the
composition of coal-swamp floras happened during the Pennsylvanian,
when the lycopod-dominated flora was replaced by a tree fern-dominated
flora, and seed plants assumed a prominent role. Carbon isotopic ratios
indicate that a C3-photosynthetic pathway analogous to that of present C3-
plants had been already developed by the Late Carboniferous–Permian
(Auras et al., 2006). Organic-geochemical investigations carried on
Devonian, Carboniferous and Permian coals in a wide palaeogeographic
scenario revealed that no significant changes in chemical composition of
the organic matter accompanied the Late Palaeozoic rapid morphologic
evolution of higher land plants (Wollenweber et al., 2006). Furthermore,
land plant organic matter from a variety of late Silurian to Late Permian
terrestrial successions was recently investigated by Peters-Kottig et al.
(2006), revealing no remarkable influences in organic carbon isotopic
composition due to climatic conditions.
Many of the most significant black shale episodes in the Palaeozoic
strictly match with major crises in the history of life. Understanding
what drives global diversity may be used to explain processes, such as
mass extinctions, that control diversity and turnover at a variety of
geographic and temporal scales. But what is the role/effect of organic
224 A. Negri et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 218–227
carbon rich sediments in extinction events? The Late Ordovician two-
phase extinction events and the multi-staged Devonian events show a
pronounced but short-lived increase of the C28/C29-sterane-ratios,
reflecting possibly the development of more opportunistic species. The
quick recovery of the ratio would indicate that, at least for the younger
crisis, the Late Devonian extinctions did not produce any lasting
fundamental changes in the assemblage of the phytoplanktonic green
algae, and the dominant phytoplankton groups regain their older
proportions. Prasinophyte algae, abundant in sediments deposited
under oxygen depleted conditions, might have quickly adapted in the
events and produced the recorded increase in C28 steranes, in analogy
with the behaviour of recent prasinophytes (Schwark and Empt, 2006).
5. Final remarks
The aim of this Special Issue is to describe and discuss Phanerozoic
OC-rich sediments while breaking the walls that have traditionally
existed between Palaeozoic, Mesozoic and Cenozoic specialists, who too
often confine and organize themselves into hermetic “time capsules”.
During the process of writing this overview and editing this Special
Issue, we have realized that some substantial problems still hamper the
Scientific Community in its approach to the study of OC-rich sediments.
In general, specialists of each Era work in completely different time
scales that range from thousands to millions of years. This generalization
implies that the “temporal magnification” through which scientists are
facing the subject varies from the fine resolution of the Modern and Late
Holocene to the extremely low resolution of the Early Palaeozoic.
Speaking metaphorically, it is like studying the same object by SEM, with
an optical microscope, or with naked eyes and comparing their results.
In addition, too often we recognized an exasperating use of the
uniformitarianism principle in which models or opinions derived from
recent examples are simplistically applied to any of the older “time-
boxes”. In actuality, physical and biological conditions (e.g., oxygen
and CO2) have strongly varied through time. Palaeozoic black shales
were clearly deposited in a CO2-dominated setting (see Berner, 1994,
1998), whereas younger deposits reflect a lower concentration of the
same gas. Again, the nature of primary producers is not yet completely
defined for pre-Jurassic production of organic matter. Furthermore,
palaeogeographic scenarios reveal completely different worlds in
terms of land masses, oceans, palaeolatitudes, etc. According to this,
any attempt to model the deposition of OC-rich sediments through the
Phanerozoic must necessarily be tuned with all these variables.
Another relevant point is that some of the Phanerozoic OC-rich
sediments are defined as global events, like the Cretaceous OAE1a and
OAE2, but some others appear to have had a more restricted and even
localized significance. Studies on OC-rich sediments have so far been
concentrated on specific areas or precise time slices (e.g., the Cretaceous
and in here even more focused on specific isotopic excursions preserved
in the sediments), while other periods of time have received much less
attention. What clearly emerges now is the urgent need of recognizing
which of these deposits are really local and which are really global
(meaning that global is independent of latitude or physiography). This
different attitude will probably require us to apply different approaches
in search of possible interpretations and perhaps diverse mechanisms
leading to the deposition of OC-rich sequences.
The three main issues described here need to be further
investigated and are certainly worth answering. They should not be
regarded as problems but, on the contrary, as opportunities for new
achievements, in particular in the light of the current discussion on
global warming. In our opinion, the Scientific Community must come
to a multiple-time scale approach and to a constructive dialogue that
better integrates data and models in order to be even more successful.
These efforts, with an emphasis on the upscaling/downscaling of
processes and effects/feedbacks, will lead to the identification of
methodologies that may be used uniformly in the Cenozoic, Mesozoic
and Palaeozoic.
If our target objective is global in nature and not restricted to any
period of time, we will be able to test the validity of Processes in the
recent as well as its application in the past, to obtain real Progress in
the knowledge of OC-rich sediments, and to gain credibility for
delineating true Perspectives for the future. That way integrated
research into OC-rich sediments from the past may provide critical
information that help to improving climate predictions into the future
beyond the IPCC time horizon.
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Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Transport and depositional process of soil organic matter during wet and dry storms
on the Têt inner shelf (NW Mediterranean)
J.-H. Kim a,⁎, R. Buscail b, F. Bourrin b,e, A. Palanques c, J.S. Sinninghe Damsté a, J. Bonnin b,d, S. Schouten a
a
Royal Netherlands Institute for Sea Research (NIOZ), Department of Marine Organic Biogeochemistry, PO Box 59, 1790 AB Den Burg, Texel, The Netherlands
b
CEFREM-CNRS UMR 5110, Université de Perpignan, 52 avenue Paul Alduy, 66860 Perpignan Cedex, France
c
Instituto de Ciencias del Mar-C.S.I.C., Passeig Maritim de la Barceloneta, 37, 08003 Barcelona, Spain
d
EPOC-UMR 5805, Université de Bordeaux 1, Avenue des Facultés, 33405 Talence Cedex, France
e
Observatoire Océanologique de Villefranche, Laboratoire d'Océanographie de Villefranche, CNRS-Université Pierre et Marie Curie, B.P. 08, 06238 Villefranche-sur-mer, France

A R T I C L E I N F O A B S T R A C T

Article history: River floods and storm waves are major processes for the dispersal and deposition of terrestrial organic
Received 30 November 2007 matter (OM) in river-dominated coastal areas. A “wet storm” is connected to a flood with a high river
Received in revised form 5 April 2008 discharge, while a “dry storm” is not associated with a flood. To better understand the sedimentation
Accepted 17 April 2008
dynamics of terrestrial OM, especially soil OM, at the land–ocean interface during wet and dry storms, we
studied sediment trap and core material collected on the Têt inner shelf (NW Mediterranean) using multiple
Keywords:
organic proxies in combination with hydrodynamic parameters. The proportion of soil OM to the total OM in
NW Mediterranean
Soil organic matter
the trap material calculated based on the BIT (Branched and Isoprenoid Tetraether) index was higher during
Têt inner shelf both wet (~ 40%) and dry (~ 30%) storms than during non-storm periods (~ 10%). However, only surface
BIT index sediments (1-cm thick layers) recovered after December wet and moderate storms in 2003 showed enhanced
Wet storm soil OM percentages compared to the deeper sediments deposited during the last century. Given that the wet
Dry storm storm eroded 4-cm of seabed at the study site, flood-induced fresh soil OM was not deposited on the Têt
inner shelf during the wet storm. However, the following moderate storm caused resuspension of flood-
associated soil OM which was previously trapped nearshore. Accordingly soil OM was transported to the Têt
inner shelf and stored there until the dry storm occurred.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Continental margins are dynamic regions where most riverine
particulate matter is deposited. Rivers associated with deltaic envi-
ronments provide an important pathway to deliver terrestrial par-
ticulate matter to the marine environment. Processes involved in
transferring riverine particulate matter to the shelf are numerous:
floods, storm waves, up and downwelling, cascading, eddies, internal
waves, etc (e.g. Dufau-Julliand et al., 2004; Fan et al., 2004;
Palanques et al., 2006). River floods and storm waves are particularly
important processes for the delivery, dispersal and deposition of
riverine particulate matter in river-dominated coastal oceans (e.g.
Ogston et al., 2000; Ahn and Grant, 2007).
A “wet storm” is connected to a flood with a high river discharge,
while a “dry storm” occurs without significant river runoff (Ogston et
al., 2000). Sediment dynamics during wet and dry storms in the NW
Mediterranean were studied (Guillén et al., 2006). An increase in
suspended sediment concentration and erosion of seabed on the Têt
inner shelf was noted during the wet storm of 4 December 2003.
⁎ Corresponding author. Tel.: +31 222 3695567; fax: +31 222 319674.
E-mail address: jhkim@nioz.nl (J.-H. Kim).
Therefore, the Têt system, a small river system characteristic of the
Mediterranean, behaves differently compared to larger systems, such
as the Eel system in the northern Pacific coast, where ephemeral
(days–weeks) fine flood layers are deposited during wet storms (e.g.
Mullenbach and Nittrouer, 2000; Wheatcroft and Borgeld, 2000; Fan
et al., 2004).
In order to study the effect of wet and dry storms on the OM
deposition in coastal areas, we performed organic geochemical ana-
lyses on sediment trap samples collected during the storm events and
surface sediments collected before and after each of these storm
events. We applied the newly developed BIT (Branched and
Isoprenoid Tetraether) index as a proxy for soil organic matter (OM)
input. The branched GDGTs are derived from bacteria predominantly
thriving in soils (Weijers et al., 2006a,b) and transported via rivers to
the ocean margin (Hopmans et al., 2004; Herfort et al., 2006).
Previous studies carried out in the Gulf of Lions and on the Têt River
(Kim et al., 2006, 2007) have shown that the branched GDGTs
detected in the Gulf of Lions were transported from land to sea by
rivers. Therefore, branched GDGTs along with long-chain n-alkanes,
compounds derived from plant leaf wax, were used here as
continental lipid biomarkers. Conversely, crenarchaeol is mainly
produced by non-extremophilic marine planktonic Crenarchaeota

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.04.019
 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238 229

Fig. 1. Map of study area showing the Gulf of Lions with main rivers and submarine canyons and detailed sedimentary map of the Têt prodelta (redrawn from the geological map of
Perpignan, 1/50,000e). The Têt POEM buoy site is located off Têt River mouth in 28 m water depth.

(Sinninghe Damsté et al., 2002), although this compound was also crenarchaeol was regarded as a marine lipid biomarker. Our approach
detected, albeit in small amounts, in terrestrial environments (Herfort based on multiple organic proxies in combination with hydrodynamic
et al., 2006; Kim et al., 2006, 2007; Weijers et al., 2006b). Therefore, parameters provided information on transport and depositional
230 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238
processes of riverine soil OM during wet and dry storms on the Têt
inner shelf.
2. Study area
The Gulf of Lions is a river-dominated continental margin located in
the NW Mediterranean between 42°N–3°E and 44°N–6°E (Fig. 1). Its
crescent shaped continental shelf is fairly broad and its continental
slope incised by numerous submarine canyons. The sediment
distribution displays a mid-shelf mud belt that follows the predomi-
nance of the Rhône River inputs and the general coastal circulation. The
inner and outer shelf regions comprise mixed sandy mud deposits
(Aloïsi et al., 1973).
The Mediterranean rivers flowing into the Gulf of Lions (e.g. Têt,
Agly, Aude, Hérault) respond quickly to variations in rainfall with
episodic water discharges. In some areas, almost all annual rainfall falls
within a few days (Ludwig et al., 2004). Therefore, the impact of storms
associated with a high precipitation on river discharge is largely
enhanced in the Mediterranean terrestrial basins. Consequently,
transport of material from land to sea by rivers is strictly conditioned
by synergic effects of storms and floods.
The Têt system, a typical Mediterranean river system, is located in the
south-western part of the Gulf of Lions (NW Mediterranean, Fig. 1). The
Têt River catchment area is about 1400 km2 (Ludwig et al., 2004). The
Fig. 2. HPLC/APCI-MS base peak chromatogram of GDGT lipids in the trap sample (I-6) and GDGT structures: I, II, and III indicate the branched GDGTs and IV is crenarchaeol.
lithology of the Têt watershed is dominated by old plutonic and
metamorphic rocks (granite, gneiss, mica schist and schist), which are
weathering resistant and only slowly mineralize (Salvayre, 1974; Garcia-
Esteves et al., 2007). Limestone is present in the middle part of the
watershed. Further downstream, the river enters in its alluvial plain which
consists of thick fillings of the erosion products of the upstream rocks that
accumulated during Pliocene and Quaternary periods. The adjacent shelf
sediments are composed mostly of sands and silts between the shoreline
and 20 m water depth and of clayey silts and silty clays between 20 m and
40 m water depth (Aloïsi et al.,1973, Fig.1). The Têt River discharges water
and sediment episodically onto the continental shelf, generating an
ephemeral prodeltaic deposit (e.g. Buscail et al., 1990, 1995).
3. Material and methods
3.1. Meteorological data
The water discharge data of the Têt River in m3 s− 1 was obtained from
the “HYDRO” data bank hosted at the French Ministry of Environment. The
hourly water discharge data of Têt River represents the sum of the water
discharge measured at the “Joffre” hydrologic station and at the Basse River,
a small affluent. Since suspended particulate matter (SPM) records for the
considered time periods in this study were not directly measured, a
previously established relationship (Bourrin et al., 2006) between SPM in
 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238
mg L− 1 and instantaneous river discharge in m3 s− 1 (Qi) was applied to the
hourly water discharge data for the study periods to obtain SPMs in mg L− 1:
logSPM ¼ 0:294llogQi2 −0:0951logQi þ 0:9839ðr2 ¼ 0:60; n ¼ 1382Þ
The SPM discharges of the Têt River were further estimated based
on the calculated SPMs (mg L− 1) and the measured river discharge data
(m3 s− 1) in ton per hour (T h− 1).
3.2. Hydrodynamic data
Temperature and salinity were measured at 1 m above bottom
(mab) with an Aanderaa RCM9 installed on a tripod frame at the Têt
buoy site. The Têt buoy site is located 3 km off the Têt River mouth at
28 m water depth and is part of the POEM-L2R (Observation Platform
of the Mediterranean Environment of the Littoral of Languedoc-
Roussillon) station maintained by CEFREM since 2003.
3.3. Sampling
A sequential cylindrical sediment trap (136 cm high with a filter dia-
meter of 15.4 cm) mounted on a tripod frame was deployed at the Têt buoy
site (28 m water depth, 42.7041°N, 3.0668°E) from 27 November 2003 to 16
December 2003 (12 bottles, 2 day collecting interval) and from 5 February
2004 to 10 March 2004 (12 bottles, 3 day collecting interval). During the
first deployment, only cups 4 to 6 were recovered in good condition while
others were either lost during recovery, or heavily contaminated by
sediment deposited on the trap carousel. During the second deployment,
the whole series of cups 1–12 were recovered in good condition.
Fig. 3. Meteorological, hydrodynamic, and sedimentological parameters: hourly water discharge of the Têt River (m3 s− 1), hourly Têt River SPM discharge (T h− 1), and near-bottom
wave orbital velocity (m s− 1) from Guillén et al. (2006), temperature (°C), salinity, and SPM concentration (g L− 1) at 1 mab at the Têt buoy site.
231
Sediment cores were recovered by divers using transparent Perspex
tubes (7 cm diameter and 20 cm long) in close vicinity of the Têt buoy
site. Cores were obtained on 26 November 2003, 12 December 2003, 11
ð1Þ February 2004, and 15 March 2004. The cores were sliced at 1-cm
intervals. The trap and core samples were freeze-dried and homo-
genized prior to analysis.
3.4. Geochemical analyses
Bulk sediment and lipid analyses were done as previously
described by Kim et al. (2006). In brief, freeze-dried, acidified
samples were analyzed for total organic carbon concentrations (TOC)
with an automatic CN-analyzer LECO 2000 at CEFREM. The precision
for TOC was 0.2 wt.%. For stable carbon isotopic compositions of TOC
(δ13Corg), acidified samples with 2 M HCl to remove carbonates were
combusted using a Flash EA 1112 Elemental Analyser interfaced with
a ThermoFinnigan DeltaPlus mass spectrometer at NIOZ. Isotope
values were calibrated to a benzoic acid standard (δ13Corg = − 27.8‰
with respect to Vienna Pee Dee Belemnite (VPDB) standard calib-
rated on NBS-22 and corrected for blank contribution. The δ13Corg
values are reported in the standard delta notation relative to VPDB
standard. The analyses were done at least in duplicate. The analytical
reproducibility was ± 0.2‰.
Total lipid contents of sediments were measured at CEFREM using
a colorimetric method (Barnes and Blackstock, 1973) after extraction
with a mixture of chloroform:methanol (CHCl3:MeOH, 2:1 v/v).
Absorption of the products resulting from the colorimetric reaction
between extract acidified with H2SO4 and a solution of Vanillin/H3PO4
was measured at 520 nm with a Beckman spectrophotometer. For lipid
232 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238

analysis, freeze-dried samples were extracted with an Accelerated
Solvent Extractor (DIONEX ASE 200) using a mixture of dichloro-
methane (DCM):MeOH (9:1 v/v). The internal standard (Huguet et al.,
2006) for GDGT quantifications was added into the total extracts
before they were separated into three fractions over an Al2O3 column
using hexane:DCM (9:1 v/v), hexane:DCM (1:1 v/v), and DCM:MeOH
(1:1 v/v), respectively. For aliphatic hydrocarbon (n-alkane) analysis,
the hexane:DCM (9:1 v/v) fractions of the total lipid extract were
further purified over an AgNO3-impregnated silicagel column using
hexane as the eluent. The internal standard (perdeutero-n-C24 alkane)
was added into the purified fractions before GC analysis and used as
reference for n-alkane quantification. Analyses were performed on a
Hewlett Packard 5890 series II gas chromatograph. For GDGT analysis,
the DCM:MeOH (1:1 v/v) fractions were analyzed with a high
performance liquid chromatography/atmospheric pressure positive
ion chemical ionization mass spectrometry (HPLC/APCI-MS). GDGTs
were detected by single ion monitoring of their [M + H]+ ions (dwell
time 237 ms) and quantification of the GDGT compounds was
achieved by integrating the peak areas and using a C46 GDGT internal
standard according to Huguet et al. (2006). Values of BIT index were
calculated according to Hopmans et al. (2004):
BITindex ¼ ½I þ II þ III=½I þ II þ III þ IV ð2Þ
The roman numerals refer to the GDGTs indicated in Fig. 2. I, II, and III
are branched GDGTs and IV the isoprenoid GDGT, crenarchaeol. The
reproducibility in the determination of the BIT index was better than 0.01.

Fig. 4. Results of bulk sediment and lipid analyses from Têt buoy site trap sediments: total mass flux (g m− 2 d− 1), TOC flux (g m− 2 d− 1), δ13Corg (‰ VPDB), ΣALK27–31 flux (mg m− 2 d− 1),
branched GDGT flux (μg m− 2 d− 1), crenarchaeol flux (μg m− 2 d− 1), and BIT index. TOC content (wt.%), total lipid (mg g−sed 1
), ΣALK27–31 (μg g−sed
1
), sum of branched GDGTs concentration
(ng g−sed
1
), and crenarchaeol concentration (ng g−sed
1
) are indicated as red coloured lines. Filled triangles indicate dates when sediment cores were taken in the Têt buoy site.
 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238 233

Fig. 5. Results of geochemical analyses from Têt buoy sediment cores: TOC contents (wt.%), δ13Corg (‰ VPDB), total lipids (mg g−sed
1
), ΣALK27–31 (μg g−sed
1
), BIT index, sum of branched
GDGTs concentration (ng g−sed
1
), and crenarchaeol concentration (ng g−sed
1
).
234 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238
4. Results
4.1. Meteorological and hydrodynamic parameters
Têt River water and SPM discharge, near-bottom wave orbital
velocity, temperature, salinity, and suspended particulate matter
concentration data are shown in Fig. 3. For the considered time
periods when sediment traps were deployed on the Têt buoy site, the
hourly Têt River water discharges ranged from 5 to 363 m3 s− 1, with
two major peaks on 4 December 2003 at 12:00 am and on 21 February
2004 at 3:00 am, respectively. The peak water discharges were 363
and 78 m3 s− 1, respectively. Floods in the Têt River are defined as a
river discharge N100 m3 s− 1 (Garcia-Esteves, 2005). Therefore, only
the first peak in water discharge on 4 December 2003 can be regarded
as a flood. It lasted for two days and supplied 2⁎104 tons of sediment to
the Têt prodelta area.
Based on the near-bottom current speed produced by surface
waves (near-bottom wave orbital velocity), two major (N1.2 m s− 1) and
two moderate (0.9 m s− 1) storm events were observed during the
study period (cf. Guillén et al., 2006). The major storm event occurred
on 4 December 2003 and was accompanied by a flood, resulting in a
“wet storm” event. However, the second major storm occurring on 21
February 2004 was not related to a flood, and therefore it is described
as a “dry storm” event although Têt River water and sediment
discharges were slightly increased. Two moderate storms took place
on 8 December 2003 and 14 March 2004. During these moderate
storms, increased Têt River water and particulate matter discharges
were not observed.
Temperature measured at the Têt buoy site abruptly dropped
(about 1 °C) during the wet storm, while there was no major change
during the following moderate storm. In general, temperatures were
lower (~ 4 °C) in February and March 2004 than in November and
December 2003. During the dry storm, temperature also dropped but
less than during the wet storm (~0.5 °C). A significant salinity drop
was recorded after the December wet and the moderate storm
Fig. 6. Calculated terrestrial OM percentages based on δ13Corg and BIT index using a two end-member model and marine, soil, and plant OM percentages using a three end-member
model for Têt trap samples. Filled triangles indicate dates when sediment cores were taken in the Têt buoy site.
following it. SPM concentration at the Têt buoy site drastically
increased during the wet and dry storms and to a lesser degree during
the moderate storms.
4.2. Sedimentology and bulk geochemistry
Total mass flux, TOC content and flux, and δ13Corg values of the
particulate matter collected with the sediment trap deployed at the
study site are shown in Fig. 4. During the major and moderate storm
events that occurred in December 2003, the total mass fluxes were
2050 g m− 2 d− 1 and 1030 g m− 2 d− 1, respectively. During the dry storm
event in February 2004, the total mass flux drastically increased up to
a value of 1710 g m− 2 d− 1. During the non-storm period, the sediment
fluxes were relatively low, varying from 2 to 340 g m− 2 d− 1.
The TOC content of the particulate matter was highest during the
December moderate storm. The TOC fluxes during the wet and dry storms
were much higher (ca. 50 and 30 g m− 2 d− 1, respectively) than during
non-storm periods, varying between 0.1 g m− 2 d− 1 and 4 g m− 2 d− 1.
δ13Corg values of the particulate matter during the wet and moderate
storms (ca. −27‰) were significantly lower than those (ca. −25‰) during
the dry storm.
The bulk parameter data (TOC and δ13Corg) of the four sediment cores
are plotted in Fig. 5. In general, TOC values were below 1 wt.%. However,
the top 1 cm layers of the cores taken in December 2003 and February
2004 showed increased values, with 3.2 wt.% and 1.7 wt.%, respectively.
δ13Corg values from the upper 5 cm varied substantially between −26.3‰
and −22.8‰, while they were fairly constant below 5 cm.
4.3. Lipid geochemistry
The lipid data acquired from the sediment trap deployed at the Têt
buoy site are shown in Fig. 4. The concentrations of total lipid (mg g−sed
1
),
ΣALK27–33 (μg g−sed
1
), and branched GDGTs (ng g−sed
1
) were highest during
the December moderate storm and were lower during the following
February dry storm. In contrast, crenarchaeol concentration (μg g−sed 1
)
 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238
Fig. 7. Calculated terrestrial OM percentages based on δ13Corg and BIT index using a two end-member model in the upper panel and marine, soil, and plant OM percentages using a
three end-member model in the lower panel for Têt sediment core samples.
was much higher during non-storm periods than during storm events.
Due to limited amounts of trap material, only four samples could be
measured for the total lipid concentration and their flux values varied
between 0.1 and 0.9 g m− 2 d− 1, showing higher fluxes during storm events,
although only one sample from a non-storm period was measured. The
flux of the summed C27 to C31 n-alkanes (ΣALK27–33 flux) varied between
0.02 and 11 mg m− 2 d− 1, with higher fluxes during storm events. The flux
of branched GDGTs, derived from soils, showed the same pattern as the
ΣALK27–33 flux, varying between 1 and 135 μg m− 2 d− 1. In general, the
crenarchaeol fluxes were higher than those of the branched GDGTs. The
crenarchaeol fluxes ranged from 6 and 286 μg m− 2 d− 1. The BIT values of
the trap samples varied between 0.08 and 0.36, with generally higher
values during storm events than during intermediate non-storm periods.
The lipid data acquired from four sediment cores are shown in Fig. 5.
The total lipid concentrations ranged from 0.1 to 1.7 mg g−sed 1
, with the
highest concentration in the sediment (0.5–1.0 cm) taken in December
2003. ΣALK27–33 concentrations were fairly constant throughout four
cores, except for the top 1 cm layers of the cores taken in December
235
2003 and February 2004. The branched GDGTs and crenarchaeol
concentrations basically followed the same pattern as the total lipid and
ΣALK27–33 concentrations. The BIT values were relatively constant (0.3 ±
0.02) throughout the cores, except for the higher BIT values (up to 0.55)
in the top 1 cm layers of the cores taken in December 2003 and
February 2004.
5. Discussion
5.1. Source and abundance of terrestrial OM in Têt sediment traps
In a previous study by Kim et al. (2007), Têt River water was
sampled at the station Perpignan from November 2000 to April 2002
and at the station Villelongue from January 2005 to February 2006.
The mean stable carbon isotopic composition of particulate organic
carbon (δ13CPOC) of the Têt River flowing to the Gulf of Lions was on
average −26.1‰ which is typical of C3 plant vegetation (e.g. Tyson,
1995; Meyers, 1997) and depleted in 13C compared to that of seawater
236 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238
sampled in the Têt prodelta (−22.7‰), the latter being, close to typical
marine δ13CPOC values (−18 to −22‰, e.g. Meyers, 1994, 1997 and
references cited therein). The δ13Corg values of the trap samples
studied here (−26.6 to −24.9‰) suggest the presence of substantial
amounts of terrestrial OM in the Têt traps. The δ13Corg values found
during the early December wet storm (4 December 2003) and the
following moderate storm (8 December 2003) were lower (− 26.6‰
and −26.5‰, respectively) than that from the February dry storm
(−25.2‰), suggesting enhanced terrestrial OM contributions during
the December storms. The BIT values of the trap samples (0.08 to 0.36)
were intermediate between those of the Têt River (0.85, Kim et al.,
2007) and of seawater (0.00, Kim et al., 2007), indicating a substantial
input of soil OM into the sediment trap, especially during the storms.
Based on the δ13Corg values, we estimated the relative proportions
of marine and terrestrial OM with a two end-member model,
assuming terrestrial (δ13Cterr = −27‰) and marine (δ13Cmar = −20‰)
OM end-members (cf. Kim et al., 2006):
TOCsample ¼ OMmar þ OMterr
δ13 Csample ⁎TOC ¼ δ13 Cmar ⁎OMmar þ δ13 Cterr ⁎OMterr
where OMmar and OMterr are the contents of marine and terrestrial
OM, and δ13Cmar and δ13Cterr are the isotopic compositions of marine
and terrestrial OM, respectively. The estimated contribution of
terrestrial OM varied between 89 and 94% in December 2003 and
between 70 and 74% in February and March 2004 (Fig. 6). During the
December wet and moderate storms, terrestrial OM contribution was
higher than that during the February dry storm.
Similar to the calculation of terrestrial OM based on the δ13Corg
values, we estimated the portions of soil and marine OM, assuming soil
(BITsoil = 0.85) and marine (BITmar = 0.00) OM end-members (Kim et al.,
2007). The estimated contributions of soil OM based on the BIT indices
ranged from 39 to 42% in December 2003 and between 9 and 31% in
February and March 2004 (Fig. 6). The BIT approach suggested relatively
higher amounts of soil OM during the December wet and moderate
storms than during the February dry storm. The trend in soil OM
abundance is similar to that of terrestrial OM based on δ13Corg values.
The estimated relative terrestrial OM amounts based on δ13Corg
values were substantially higher than the soil OM estimates based on
BIT values (see Fig. 6). Likely, the δ13Corg comprises both soil and
vegetation OM. In addition, ancient refractory sedimentary OM, which
has a depleted 13C value (e.g. Blair et al., 2003; Hwang et al., 2005), may
be a significant component of suspended loads in small mountainous
rivers and some marine sediments. However, there are no sedimentary
rocks in the Têt watershed containing high percentages of organic
carbon which could have contributed to the high terrestrial OM
portions observed in the Têt trap samples. A sewage treatment plant is
located above the Têt river station (see Fig. 1). Therefore, anthropo-
genic OM input possibly also influenced the relative terrestrial OM
estimations based on the δ13Corg. However, it is impossible at this stage
to estimate the portion of this source due to the lack of data.
We thus combine the BIT index with the δ13Corg to estimate relative
proportions of marine, soil, and plant OM using a three end-member
model in a similar way as conducted by Gordon and Goñi (2003):
TOCsample ¼ OMmar þ OMsoil þ OMplant
δ13 Csample ⁎TOCsample ¼ δ13 Cmar ⁎OMmar þ δ13 Csoil ⁎OMsoil
þ δ13 Cplant ⁎OMplant
BITsample ⁎TOCsample ¼ BITmar ⁎OMmar þ BITsoil ⁎OMsoil
þ BITplant ⁎OMplant
OMmar, OMterr, and OMplant are the relative amount of marine, soil,
and plant OM, respectively. The end-member values of δ13C and BIT are
as follows: δ13Cmar =−20‰ (Fry and Sherr, 1984), δ13Csoil = −26‰ (Powers
and Schlesinger, 2002), δ13Cplant =−28‰ (Hedges et al.,1986), BITsoil =0.85
(Kim et al., 2007), BITmar =0.00 (Kim et al., 2007), BITplant =0.00 (Hopmans
et al., 2004; Weijers et al., 2006b). These calculations show that the
estimated percentages of terrestrial OM (comprising both soil and plant
OM) are quite substantial relative to those of marine OM (67 to 92%,
Fig. 6). Furthermore, a substantial part of total OM is comprised of soil
OM during the storm events (31 to 42%, Fig. 6).
5.2. Source and distribution of terrestrial OM in Têt inner shelf sediment
The surface sediments (1-cm thick layers) recovered after the wet
and moderate storms in December 2003 showed enhanced TOC, BIT
values and lipid concentrations and lower δ13Corg values compared to
those from the surface sediments collected before the wet storm and
after the dry and moderate storms. This indicates that the terrestrial
ð3Þ OM fraction was enhanced in the surface sediments sampled in
December 2003 and February 2004. Terrestrial OM estimates based on
δ13Corg and BIT values using a two end-member model (see above)
ð4Þ
confirmed increases in terrestrial OM proportions after the wet and
moderate storms in December 2003 compared to those before the
December wet storm in 2003 as well as after the February dry storm
and the March moderate storm in 2004 (Fig. 7). The estimated
percentages of soil OM using a three end-member model (see above)
suggest that a large part of total OM is comprised of soil OM (up to
65%) after the wet and moderate storms than before the wet storm
and after the dry and moderate storms (28 to 33%; Fig. 7).
Differences in bulk and lipid parameters were also observed below
the sediment surface layers (Fig. 5). For example, sediments from 1 to
4 cm depth were depleted in TOC (0.2 wt.%) and total lipids (0.05–
0.07 mg g−sed 1
) after the February dry and March moderate storms,
compared to the lower sediments down to 10 cm (TOC 0.5–0.6 wt.%.
and total lipids 0.12–0.14 mg g−sed1
). Likewise, considerable variations
were recorded in δ Corg. In general, the δ13Corg values of the layers
13
from 1 to 4 cm were enriched in 13C with an average value of −23.8‰,
while the lower parts down to 10 cm had the average value of −25.0‰.
This suggests relatively higher abundance of terrestrial OM in the
lower parts of the sediment cores possibly because terrestrial OM is
better preserved (e.g. Hoefs, et al., 2002; Burdige, 2007). The layers of
higher δ13Corg values were accompanied by slightly lower TOC and
total lipids contents but no significant changes were observed in other
lipid parameters.
Estimated terrestrial OM percentages based on the δ13Corg values
varied between 40% and 80%. This is at least twice as high as soil OM
percentages based on the BIT values, ranging from 20 to 40% (Fig. 7). In
present day hydrodynamic conditions, flood-associated fine sedi-
ments freshly deposited do not remain in place more than 2 months
on the Têt prodelta area (Bourrin et al., 2007). Therefore, δ13Corg
approaches seem to overestimate the proportion of terrestrial OM on
the Têt inner shelf. As mentioned above, this may lie partly in the
assumed end-member values of δ13Corg. However, the differences
between estimated terrestrial OM based on the δ13Corg and soil OM
based on the BIT index are likely largely due to the large OM
contribution from contemporary terrestrial vegetations such as lignin
(e.g. Hedges and Mann, 1979; Da Cunha et al., 2001).
ð5Þ The trends of estimated contributions of plant OM using a three
end-member model were significantly different compared to those of
soil OM. In general, the layers between 1 cm and 4 cm contained lower
plant OM percentages compared to the lower part down to 10 cm,
ð6Þ while soil OM percentages were fairly constant. This implies that
relatively labile, 13C enriched organic compounds of terrestrial OM
were selectively remineralized in the lower part (4–10 cm) of the
sediment cores on the Têt inner shelf. Studies by Wang et al. (1998)
ð7Þ and Hwang et al. (2005) showed that in general lipids are more
 J.-H. Kim et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 228–238
refractory than other organic compound classes, e.g. total hydro-
lysable amino acid (THAA) and total carbohydrate (TCHO). In their
studies, THAA and TCHO have higher δ13C values than those of lipids.
This suggests that selective degradation of THAA and TCHO could have
caused lower δ13C values in the lower part of sediment cores on the
Têt inner shelf, which in turn increased the estimated portions of plant
OM percentages.
5.3. Deposition of terrestrial OM on the Têt inner shelf
The wet storm of early December was associated with the highest
water and sediment discharges of the Têt River into the prodelta and
the highest suspended sediment concentration and total mass flux in
the sediment trap within the time frame of this study (Fig. 3).
However, Guillén et al. (2006) and Bourrin et al. (2007) observed that
during this December wet storm there was no flood deposit but
erosion on the Têt inner shelf. The fresh water intrusion on the Têt
inner shelf related to this wet storm can be traced by an abrupt drop of
salinity which occurred after the wet storm. This suggests that fresh
riverine OM was not delivered to the Têt buoy site during the wet
storm but only after the storm. The higher flux of terrestrial OM during
the wet storm was due to wave resuspension of terrestrial OM which
was deposited nearshore and on the Têt inner shelf prior to the
December wet storm rather than direct flood flux occurred during the
December wet storm.
Four hours after the peak of the wet storm, a 1-cm thick fluffy flood
layer was accumulated on the Têt inner shelf and the moderate storm that
occurred after the wet storm caused about 4-cm thick deposition of
resuspended flood-associated sediment (Guillén et al., 2006). This in-
dicates that enhanced terrestrial OM signals of the top 1-cm layer of the
sediment core sampled in December 2003 and February 2004 (Fig. 7) were
not direct flood deposit but rather flood-associated storm deposit. The
Rhône River has high mean SPM discharge of about 7–10⁎106 106 T yr− 1
(Sempéré et al., 2000; Pont et al., 2002), accounting for ~80% of the riverine
inputs to the Gulf of Lions (Durrieu de Madron et al., 2000). Considering
this large contribution of terrestrial OM through the Rhône River, the high
terrestrial OM layer on the Têt inner shelf was probably formed both by the
supply from the Têt River and from other rivers located northwards of the
Têt River, e.g. Aude, Hérault, Rhône Rivers (Fig. 1). Especially, the floods
associated to one single SE windstorm event (wet storm) are generally
concomitant in the whole Gulf of Lions. For example during the December
wet storm in 2003, all the rivers flowing into the Gulf of Lions generated a
big flood and especially the Rhône River delivered large amounts of water
(10,000 m3 s− 1, Palanques et al., 2006) and terrestrial material to the
coastal zone (Antonelli et al., 2008). Such terrestrial material was trapped
nearshore and resuspended and further transported southwards during
the moderate storm, forming high terrestrial OM layer on the Têt inner
shelf (Guillén et al., 2006).
When time passed, fine terrestrial OM on the Têt inner shelf was
diluted by marine production and thus terrestrial OM proportion was
reduced on the Têt inner shelf. This dilution process can be traced in
the core top sediment taken in February 2004 which showed a lower
proportion of terrestrial OM (88%) compared to that of the December
core top sediment (95%). After the dry storm, no flood layer was
deposited and the moderate storm (15 March 2004) finally occurred
enhancing sediment erosion down to 1 cm depth. As a result, after the
dry and moderate storms, the core top from March 2004 has a rela-
tively lower proportion of terrestrial OM.
Besides the top 1-cm flood layers, the lower sediment layers con-
sisted of very-fine, well-sorted sands (Bourrin et al., 2007). Radio-
carbon dating of T. communis shells of these layers and 210Pb dating
showed similar ages from 1836 to 1950 (modern) and thus indicate
that these layers were formed not continuously during a period of
about one century. No layers with enhanced terrestrial OM were found
related to catastrophic flooding of the last century (e.g. 1940) in the
sedimentary records, suggesting this flood layer has been eroded. The
237
decrease of sediment supply by rivers due to climate change and/or
human activities (irrigation, damming, e.g. the Vinca damm on the Têt
River was built in 1975) may have induced a winnowing of fine
material and thus a coarsening of upper sediment layers on the Têt
inner shelf.
6. Conclusions
Our study performed on the Têt inner shelf supports that the BIT
index is a useful proxy to trace flood-associated storm events in river-
dominated continental margins such as the Gulf of Lions in the NW
Mediterranean and to better understand riverine soil OM transport
and depositional processes from rivers to oceans. The Têt inner shelf
did not accumulate terrestrial OM directly during the wet storm, when
erosion was dominant at the study site but during the next moderate
storm, the flood-associated terrestrial OM was resuspended nearshore
and transported to the Têt inner shelf where it was stored until the dry
storm occurred. As a result, the small Têt system acts as a bypass area
of terrestrial OM supplied by rivers mainly during the wet storm-
associated floods and redistributed during following storms. Conse-
quently, our study supports the previous results by Guillén et al.
(2006) that the small Têt system behaves differently compared to
larger systems where during wet storms a pluricentimetric flood layer
deposition is frequently observed on the inner shelf. The BIT index
may be more useful to trace past flood events in a larger system where
the sediment deposition is continuous due to high sedimentation
rates in contrast to the small Têt system.
Acknowledgements
We would like to thank G. Jeanty, J. Carbonne, and G. Saragoni at
CEFREM, E. Hopmans, J. Ossebaar, and M. Kienhuis at NIOZ, and J. Guillén
at CSIC for the sample preparation and analytical support. We ac-
knowledge constructive reviews by two anonymous reviewers. This
study was supported by a Marie Curie Intra-European Fellowship grant
to J.-H. Kim and the EUROSTRATAFORM project funded by the European
Union.
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / p a l a e o

Geochemical evidence for high-resolution variations during deposition of the

Holocene S1 sapropel on the Cretan Ridge, Eastern Mediterranean
G. Gennari a,⁎, F. Tamburini b, D. Ariztegui c, I. Hajdas d, S. Spezzaferri a
a
University of Fribourg, Department of Geosciences, Earth Sciences, Ch. du Musée 6, 1700 Fribourg, Switzerland
b
Institute of Plant Nutrition, ETH Zurich, Eschikon 33, 8315 Lindau, Switzerland
c
University of Geneva, Section of Earth Sciences, Rue des Maraîchers 13, 1205 Geneva, Switzerland
d
Ion Beam Physics, PSI and ETH Zurich, Schafmattstrasse 20, 8093 Zurich, Switzerland

A R T I C L E I N F O A B S T R A C T

Article history: Major and minor element distributions and solid phase phosphorus contents were measured in a sediment
Received 25 January 2008 core from the Cretan Ridge that contains the Holocene S1 sapropel. Micro-XRF ultra-high resolution analysis
Received in revised form 6 June 2008 reveals multiple Mn peaks in the oxidized upper portion of the sapropel, which implies either a non-steady-
Accepted 10 June 2008
state upward remobilization of Mn or not constant downward diffusion of bottom water oxygen. Sequential
extraction allowed the identification of different phosphorus phases. Detrital phosphorus increases in the
Keywords:
Sapropel
sapropel layer, suggesting enhanced delivery from land during sapropel deposition. Higher organic carbon to
Chemical elements organic phosphorus ratios in the sapropel indicate enhanced regeneration of phosphorus relative to carbon
Phosphorus under low-oxygen conditions. Fourier analysis on the ultra-high resolution XRF data reveals frequencies that
Cycles are provisionally assigned to millennial to decennial solar cycles. Although these cycles have been reported
from several continental and marine archives, they have never been documented from Sapropel S1 in the
Eastern Mediterranean.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction 2) increased Nile river runoff linked to the periodic enhancement

The Eastern Mediterranean Sea is characterized by the occurrence
of organic matter-rich layers, termed sapropels. According to the
original definition by Kidd et al. (1978), sapropels are well-delimited
layers within open marine sediments, with thickness N1 cm and
organic carbon content N2%. The relatively high organic carbon
content of a sapropel is due to the combination of enhanced supply
and limited degradation of organic matter at the sediment–water
boundary, which is water-depth dependent (Murat and Got, 2000).
Thereby, the difference between the organic carbon content of a
sapropel and that of the surrounding sediments seems to be a more
suitable parameter to define these layers (Murat, 1991; Ariztegui et al.,
2000).
Among the various processes that have been invoked to explain
sapropel formation (see Rohling, 1994 for a review), the “stagnation/
anoxia” and the “increased productivity” models are the most
discussed. According to the stagnation/anoxia model, anoxic bottom
conditions are caused by a strong stratification of the water column
that prevents vertical mixing and oxygen supply to the bottom waters.
Different explanations have been proposed for the origin of this
stratification: 1) Eurasian ice-sheet melt water entering the Medi-
terranean Sea (Olausson, 1961; Ryan, 1972; Aksu et al., 1995);
⁎ Corresponding author. Fax: +41 26 300 97 42.
E-mail address: giordana.gennari@unifr.ch (G. Gennari).
of the African–Asian monsoons (Rossignol-Strick 1983, 1985);
3) increased rainfalls and river discharge along the northern part of
the Eastern Mediterranean Sea (Cramp et al., 1988; Rohling and
Hilgen, 1991).
In the “increased productivity” model, sapropel deposition is
linked to enhanced organic matter flux (Calvert, 1983; Calvert et al.,
1992), since the present production of organic matter in the eastern
Mediterranean cannot account for the high values of organic carbon
(TOC) characterizing these layers (Calvert, 1983).
According to other authors (Castradori, 1993; Rohling, 1994; Emeis
et al., 1998; Emeis et al., 2000), an increase of nutrient input via river
runoff could have caused enhanced primary production and also
promoted the stratification of the water column, coupling the two
models. A significant increase of productivity at times of sapropel
deposition is also revealed by paleo-productivity proxies, as Ba
and marine barite concentration (e.g., Thomson et al., 1995, 1999;
Martinez-Ruiz et al., 2000, 2003; Gallego-Torres et al., 2007).
Enhanced productivity has also been explained with a radical change
in the Mediterranean Sea circulation, from the modern anti-estuarine
to an estuarine circulation (Sarmiento et al., 1988; Howell and Thunell,
1992). Results of recent modeling studies on thermohaline circulation
suggest that a weakening of the present-day anti-estuarine circulation
can lead to the deposition of enough organic carbon to account, at
least, for the formation of the youngest sapropel S1 (Myers et al.,
2000; Stratford et al., 2000). Uncertainties still exist regarding the

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.06.007
240 G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248

extension of the anoxic/dysoxic layer in the water column; this layer Table 1
has been described as a large water mass extending below the mixed Results of AMS 14C dating on planktonic foraminifers. Calibration using OxCal 3.10
(Bronk Ramsey, 2005)
layer (Murat and Got, 2000; Stratford et al., 2000), as well as an
“anoxic blanket” above the sediment/water interface (Casford et al., Lab code Depth Material 14
C age Calibrated age
2003). More recently, Bianchi et al. (2006) suggest that a modified (cm) (yr BP) (yr BP)
thermohaline circulation supplying oxygen only to the first 500 m of ETH-34228 1.0–2.0 Mixed planktonic foram 1050 ± 55 610 ± 70
the water column may be responsible for the development of an ETH-34229 22.0–22.5 Globigerinoides ruber 6165 ± 80 6570 ± 180
anoxic blanket at the sea-floor, when coupled with higher productiv- ETH-34230 44.5–45.5 Globigerinoides ruber 11910 ± 110 13405 ± 235
ity in the euphotic zone. ETH-34231 67.5–68.0 Globigerinoides ruber 17200 ± 160 19925 ± 375

Regardless of the mechanism that led to their formation, sapropel
occurrence is cyclic and is thought to be linked to minima in the
precession cycle, corresponding to Northern Hemisphere summer
insolation maxima, with a periodicity of about 21 kyr (Rossignol-
Strick, 1983, 1985; Hilgen, 1991; Lourens et al., 1996).
In this research, we present a high-resolution geochemical study of
sapropel S1, since any change in environmental or climatic conditions
is reflected in major and minor element abundances (e.g., Wehausen
and Brumsack, 1998). Furthermore, because our proxy data offer a
very detailed and continuous record, the identification of high-order
cyclicities is attempted.
2. Materials and methods
Gravity core SIN97-01GC was collected on the morphological high
between Crete and the Peloponnesus (35°49′07″ N, 22°42′02″ E;
water depth 933 m) during the 15/97 cruise of R/V Urania (Fig. 1).
Sampling for this study was limited to the uppermost part of the core
(section 1; 0.0–68.0 cm bsf), since it contains a thick sapropel S1
overlaid by a few centimeters-thick oxidized interval, both inter-
bedded in a hemipelagic muddy succession.
Sediment samples of 0.5 cm thickness for geochemical analyses
were taken along the core at 3 cm spacing; a contiguous sampling was
also performed at any change in sediment type or color. Sediments
were then dried at room temperature and split into sub-samples. An
aliquot of the material was gently ground in an agate mortar and
passed through a sediment sieve (b125 μm), with the minimal extent
of grinding necessary to achieve this size.
A reservoir effect of 400 years was subtracted.
2.1. Organic matter
Organic matter characterization was performed at the University of
Neuchâtel on about 80 mg of ground and sieved sediment with a Rock-
Eval 6, using the standard whole rock pyrolysis method (Espitalié
et al., 1986).
2.2. Phosphorus
Phosphorus was extracted from the dried sediment after grinding
to b125 μm. A 5-step sequential extraction technique was used to
distinguish among different phosphorus sedimentary phases (SEDEX
method; Ruttenberg, 1992; Tamburini et al., 2002). Solid phases were
progressively dissolved by using a series of extractants, each chosen in
order to extract phosphorus associated with well defined sedimentary
components: (1) loosely-bound P adsorbed on mineral surfaces,
(2) iron and manganese oxy-hydroxides (referred in the text as CDB-
P), (3) authigenic apatite, (4) detrital material (igneous, metamorphic
and “aged” authigenic apatite), and (5) organic matter. The obtained
sample solutions were diluted in milli-Q water and a color developing
agent was added to the solutions following the ascorbic acid method
for phosphate (Eaton et al., 1995). All the concentrations were then
measured using a Perkin Elmer UV/Vis Spectrophotometer Lambda 10
at the GEA lab (University of Neuchâtel).

Fig. 1. Location map of core SIN97-01GC.

 G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248
Fig. 2. Corg (weight %) and elemental ratios (versus Al, Fe or Ca). Elemental ratios were smoothed using a 10 points mobile average in order to highlight the dominant trends in the data. Ox S1:oxidized sapropel S1; S1: visual dark-colored
sapropel S1.

241
242 G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248
Because of the reduction of Fe by dithionite and subsequent
complexation by citrate, during the second step of this extraction it is
possible to separate also ferric Fe (CDB-Fe). CDB-P and ferric Fe
concentration were measured using a ICP-OES at the Soil Chemistry
Institute of the ETH Zurich.
2.3. Elemental analyses
Ultra high-resolution qualitative analyses of major and minor
elements (Mn, Fe, Ca, Mg, Al, Sr, Cl, Ti) were performed on macroscopic
contiguous samples by X-ray microfluorescence (µ-XRF), using
an EDAX Eagle III XPL μprobe (40 kV, 400 μA, 50/55 Dtm) with an
analytical spot size of 50 μm. Average spacing between analytical
points was 0.35 mm. Two profiles were acquired on two different
sets of samples, giving consistent results. The µ-XRF elemental
analyses were carried at the Section of Earth Sciences of the University
of Geneva.
14
2.4. AMS C dating
Radiocarbon ages were obtained using accelerator mass spectro-
metry (AMS) technique. The 14C dating was performed at the AMS
facilities, ETH and PSI in Zurich (Table 1). Four selected samples
each containing 700 to 1000 specimens of planktonic foraminifers
(15–18 mg of pure calcium carbonate) were hand-picked under a
binocular microscope and then ultrasonically cleaned to remove
any kind of contamination and/or diagenetic alteration. Samples
were then dissolved in concentrated phosphoric acid (Hajdas et al.,
2004a). The resulting carbon dioxide was then converted into
graphite as described by Hajdas et al. (2004b). A reservoir age cor-
rection of 400 years (Siani et al., 2000) was applied to the obtained
radiocarbon conventional ages, which were then calibrated using the
program OxCal 3.10 (Bronk Ramsey, 2005).
Fig. 3. Corg (wt%) concentration and HI (mg HC/g Corg), as determined by Rock-Eval, and
Corg/Porg (molar ratio) curve.
Fig. 4. S2 versus Corg diagram for S1 samples. Boundaries between the three kerogen
type fields (dashed lines) from Langford and Blanc-Valleron (1990). Regression curve
(solid line) and migrated regression curve (dotted line) are also shown.
2.5. Fourier analysis
Four AMS 14C ages (calibrated) were used to infer sedimentation
rates and construct the chronological framework of the studied
sedimentary sequence. To identify potential high-frequency cycles
within the sedimentary record, Fourier analysis was performed on
the obtained µ-XRF elemental ratio dataset (average of 33 points
per cm). The Fourier analysis was carried out on selected elements
versus Al ratios by using the software Analyseries (Paillard et al.,
1996).
3. Results
3.1. Organic matter characterization by Rock-Eval
Organic carbon content in the studied core is generally low, but
shows a remarkable increase in correspondence with the visual dark-
colored sapropel (Fig. 2). Values range between 0.06 and 0.16 wt%
in the “normal” hemipelagic sediments and from 0.39 to 0.89 wt%
in sapropel S1.
Tmax (420 °C on average) and hydrogen index (HI) values suggest
that the organic material in sapropel S1 is mainly composed of
partially degraded marine organic matter. Low HI values (75–200 mg
HC/g C org; Fig. 3) could indicate a strong mineral matrix
effect (Espitalié et al., 1986). The S2 versus Corg diagram (Fig. 4)
confirms the presence of such matrix effect. In fact, according to
Langford and Blanc-Valleron (1990), the regression line in a S2
versus Corg diagram should pass through the axes origin, and a
positive x-intercept, as in this case, could indicate the presence of
rock-matrix effect. The high correlation degree of the samples in the
S2 versus Corg graph seems to indicate a common origin of the
organic material. In fact, if the matrix effect is eliminated by
migrating the regression line towards the axes origin, all the
sapropel S1 samples fall in the marine organic matter field (type II
kerogen field). Even though these results suggest that the main
component of the organic material characterizing sapropel S1 is of
marine origin, we do not exclude the contribution of terrestrial
material. The amount of TOC in samples below and above the visual
sapropel (b0.16 wt%) is too low, so it is not possible to distinguish
the effect of clay mineral absorption.
 G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248
Fig. 5. Percentages of total P in the analyzed phosphorus sedimentary phases.
3.2. Phosphorus
Phosphorus extracted from sediments is dominated by the
authigenic phase (apatite) that accounts on average for the 45% of
total phosphorus (calculated as the sum of the extracted phases;
Fig. 5). Both loosely-bound P and detrital P profiles (Fig. 6) show a
general down-core increasing trend, while the organic-bound P is
characterized by an opposite trend. Higher concentrations of detrital
and, to a lesser extent, of organic-bound P are observed in the core
interval between 28 and 44.5 cm bsf, corresponding to the visual
sapropel. The sapropel S1 is also characterized, in the uppermost part,
by a peak in CDB-P and in CDB-Fe. In this interval, CDB-P represents
the most abundant solid phase (up to 37% of total P, Fig. 5).
The molar Corg/Porg (Fig. 3) is higher in the sapropel (200–500) in
comparison to the overlying and underlying hemipelagic sediments
(25–130). The sediments below S1, however, show Corg/Porg values
slightly higher then the sediment above due to the general decreasing
trend of organic-bound P.
3.3. Sediment geochemistry
The chemical characterization is presented as element/Al ratios
(Fig. 2) in order to compensate for carbonate dilution (Wehausen and
Brumsack,1998). Fe, Mn and Al concentration curves are also shown for a
comparison (Fig. 7). The Mn/Al ratio shows a remarkable increase at the
top of the visual sapropel S1, developing a series of well-distinguished
peaks in the oxidized part of the sapropel. The Fe/Al ratio shows a
positive shift in the uppermost part of S1 and in the above 5 cm. Cl/Al and
Ti/Al are both enriched in the core interval corresponding to the original
sapropel (S1 + Ox S1). Ca/Al and Mg/Al are covariant too, but with an
opposite trend, and show depletion in the same interval. The Ca/Fe and
Ca/Ti ratios decrease in the whole original sapropel interval, while Sr/Ca
curve shows a positive shift in the same core interval.
243
3.4. 14C chronology
Age assessment of core SIN97-01GC is based on four AMS 14C ages
obtained from planktonic foraminifers. The shallower sample (1–2 cm
depth) was too small for monospecific dating, therefore mixed
planktonic foraminifers were picked. Both radiocarbon conventional
ages (referred in the text as 14C yr) and calibrated ages (2σ error;
referred as cal yr BP) are shown in Table 1.
The sediments immediately below the base of S1 sapropel
are dated at 11910 ± 110 14C yr BP (corresponding to 13405 ±
235 cal yr BP), while the sample immediately above the top of the
oxidized S1 displays an age of 6165 ± 80 14C yr BP (corresponding to
6570 ± 180 cal yr BP). Although there is general agreement in con-
sidering S1 to have been formed at around 9000–7000 years BP
(see Fontugne et al., 1994 for a review), several authors reported
older ages for the onset of the conditions leading to the formation
of this anoxic layer (e.g., Troelstra et al., 1991; Howell and Thunell,
1992). In particular the age of the base of S1 in core SIN797-01GC
is consistent with the ones reported by Rohling et al. (1993) for core
T87/2/20G (11680 14C yr BP; 13300 cal yr BP reported in Hayes et al.,
1999) and by Anastasakis (2007) for the south-eastern Mediterra-
nean Sea.
The top of the visual sapropel has an inferred age of 7600 14C yr BP
(corresponding to 8340 cal yr BP), well in agreement with the widely
reported dating (Rohling, 1994; Mercone et al., 2000).
3.5. Fourier analysis
The sedimentation rate was calculated by fitting a regression line
of calibrated ages against depth (Fig. 8). The calculated sedimentation
rate is constant at 3.4 cm/kyr.
The performed spectral analysis shows well-distinguished peri-
odicities with statistically significant peaks at 85–70, 60 and 50 years.
 244
G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248
Fig. 6. Phosphorus solid phases content (in μmol P/g) and CDB-Fe (in μmol Fe/g). Ox S1:oxidized sapropel S1; S1: visual dark-colored sapropel S1.
 G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248 245

increasing with increasing location depth, has been clearly established

by Murat and Got (2000). According with these authors, differences in
organic carbon concentrations are more likely the result of variations
in organic matter degradation than in organic matter availability, and
are linked to lower degradation rates or to higher burial efficiency at
deeper sites, resulting in increasing TOC content with depth. In this
framework, the low TOC content of S1 on the Cretan Ridge fits well
with the relatively shallow depositional environment (933 m).
As a consequence of the reduced preservation of organic matter,
also the HI values are relatively low, as shown by the Rock-Eval results;
this is in agreement with the positive linear correlation between HI
and TOC concentration as also reported by Bouloubassi et al. (1999) for
Pliocene–Pleistocene sapropels.

4.2. Phosphorus phases and C/P ratios

CDB-P and CDB-Fe show a peak at the top of S1, and not above the
visual sapropel, as it was expected (Slomp et al., 2002, 2004). This is
probably due to the presence of well-crystallized Fe oxides in the
oxidized sapropel (Slomp et al., 1996) that are a less efficient sink for
phosphorus in comparison with amorphous phases. The observed Fe
enrichment can then be attributed to dissolution of amorphous Fe
sulfides during the CDB step of the sequential extraction (Slomp et al.,
1996). Both CDB-P and CDB-Fe curves, however, resemble closely the
distribution shown by Slomp et al. (2002, 2004) suggesting that these
peaks could anyway be related to the redox front.
Although the detrital P fraction extracted by the SEDEX method is
operationally defined (Ruttenberg, 1992), and the extraction solution
used (1 M HCl) might also dissolve sedimentary phases (e.g., clay and
Fe minerals) that have resisted previous steps, we are confident that
this fraction well represents detrital input. In fact, the amount of P
contained in clays is negligible (Ruttenberg, 1992), and dithionite and
citrate (step II) are the most efficient extractants for Fe oxides (Slomp
et al., 1996). Generally, only well well-crystallized oxides might persist
after this step, but these would probably also be of detrital origin.
Previous studies have shown that the detrital P well correlates
with other detrital proxies, such as quartz and ice rafted debris
(e.g. Tamburini et al., 2002, 2003) which were independently mea-
sured. Considering that, and knowing that detrital P is not involved in

Fig. 7. Fe, Mn and Al concentrations (counts/second). All curves were smoothed using a
10 points mobile average in order to highlight the dominant trends in the data. Ox S1:
oxidized sapropel S1; S1: visual dark-colored sapropel S1.

Millennial and centennial periodicities are also observed though not

significant above the 95% confidence limit (see Fig. 9).

4. Discussion

4.1. TOC content and organic matter preservation

The visual dark dark-colored S1 sapropel from core SIN97-01GC is

characterized by a TOC content distinctively higher than in the
uppermost and lowermost sediments. The displayed values, ranging
from 0.39 to 0.89 wt%, are however well below the 2% organic carbon
content originally used to define these anoxic layers (Kidd et al., 1978).
Indeed, lower TOC contents have been widely reported for sapropel S1
in the Eastern Mediterranean (e.g., Murat and Got, 2000). A linear
relationship between TOC percentages and water depth, with values Fig. 8. Calibrated 14
C ages versus depth. Linear regression line is plotted.
246 G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248

Fig. 9. Fourier analysis on Mg/Al, Mn/Al, Ca/Al, Sr/Al, Ti/Al and Fe/Al curves (B-Tuckey Spectrum, Bartlett window. Bandwidth: 0.0002522. Error estimation on Power spectrum:
0.546215 b ΔP / P b 2.55813). Sedimentation rates obtained by the regression curve of the calibrated ages versus depth plot.

biological P cycling, we consider its variations mainly as an indication
of changes in detrital supply. In this case, its distribution indicates an
increase of detrital input during sapropel S1 deposition, as also
suggested by the slight increase of Ti/Al ratio in the core interval
corresponding to the original sapropel.
Organic-bound P does not positively correlate with organic C.
Because the organic matter in the sapropel is mainly of marine origin,
as corroborated by our results and widely reported for the Eastern
Mediterranean (e.g., Emeis et al., 1996), we can use a C/P Redfield ratio
of 106–117 (Redfield et al., 1963; Anderson and Sarmiento, 1994) as a
reference value for the original C/P ratio. In sapropel S1, Corg/Porg
values are higher than the expected Redfield ratio, ranging from 200
to 500, while they display lower values in the overlying and un-
derlying sediments (b 130). Our data are consistent with an enhanced
 G. Gennari et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 239–248
regeneration of P in respect to C during sapropel deposition (Ingall
and Jahnke, 1994; Slomp et al., 2002). The difference between the
observed Corg/Porg values and the one reported by Slomp et al. (2002;
Corg/Porg = 300–1085 mol/mol) is consistent with the poor organic
matter preservation evident in the low TOC and HI values.
4.3. Post-depositional alteration of sapropel S1
The geochemical signature of sapropel S1 from the Cretan Ridge is
consistent with an active post-depositional oxidation due to the
transition between different bottom water oxygenation levels at the
end of the sapropel deposition (e.g., Thomson et al., 1999). Mn/Al
peaks, and to a lesser extend the enrichment of Fe/Al observed in the
oxidized sapropel, are linked to the downward penetration of the
oxidation front (Van Santvoort et al., 1996), that led to post-
depositional removal of organic matter, as evidenced in the upper-
most part of the original sapropel. Nevertheless the Mn/Al profile
shows a more articulated shape than the characteristic double peaks
so far widely described (overview in Thomson et al., 1999). Van
Santvoort et al. (1996) already illustrated the importance of sampling
resolution in order to detect early diagenetic signals. As a case study,
they showed the different shape of the solid phase Mn profile at low (1
peak; from 1 to N2.5 cm resolution) and high high-resolution (0.5 cm)
sampling (2 peaks) (boxcore BC 12, Eastern Mediterranean). With a
ultra-high resolution (0.3 mm), our Mn/Al curve shows multiple peaks
that may derive from a non-constant upward flux of dissolved Fe2+
and Mn2+ and/or from a non-constant downward diffusion of bottom
water oxygen, probably linked to rapid and short-lasting variations in
sedimentation rates.
The Fe/Al curve presents a broad positive shift with respect to
background values, because of increased amount of Fe-oxy-hydro-
xides (Ox S1) and of pyrite or other amorphous Fe-sulfates (from the
top of the visual sapropel down to about 35 cm).
The Cl/Al profile may provide further evidence of the sapropel
original thickness, being linked to the higher porosity that usually
characterizes organic-rich sediments (Thomson et al., 1995).
The negative shift in Ca content with respect to both Fe and Sr can
be related to differences in calcite preservation and abundance of Sr-
rich aragonite, in S1 and in normal pelagic sediments.
4.4. High-frequency cyclicity
Millennial to decennial-scale periodicities have been observed at
very different locations, in both marine and continental archives (e.g.,
Hulu cave, China; GISP2 and GRIP ice cores, Greenland; monsoon
climate in Africa) and using different proxy records (see Tyson et al.,
2002). Their origin is certainly related to solar activity (Bond et al.,
2001), but the mechanisms of the complex interplay between sun and
climate are still under debate (Beer et al., 2000; Bond et al., 2001;
Turney et al., 2005).
Also in core SIN97-01GC, the Fourier analysis performed on the
ultra-high resolution elemental ratio records reveals the presence of
well-distinguished millennial to decennial cyclicities centered at
around 1700, 550, 210, 85–70, 60 and 50 years (Fig. 9). The cycles
detected in our records at 210 yr (Suess Cycles) and 85–70 yr
(Gleissberg Cycles) are most likely related to solar variability (see
Chambers et al., 1999 for a review). The 550 years periodicity has been
detected in the Holocene GISP2 ice core (Greenland; Stuiver et al.,
1995) and in North Atlantic sediment records (Chapman and
Shackleton, 2000), giving indication of an interconnection between
atmospheric and oceanic variability (Chapman and Shackleton, 2000).
According to other authors (e.g., Debret et al., 2007) solar forcing could
be a more probable explanation for these periodicities.
The 1700 years periodicity corresponds to the ∼1800 yr frequen-
cies already identified in lake sediment records, and it has been
attributed to variation in insolation (Skilbeck et al., 2005).
247
Considering the known influence of changes in insolation in the
Mediterranean and northern African region and their direct link to
sapropel formation (e.g. Rossignol-Strick, 1985), the presence of these
cycles confirms the strong sensitivity of Mediterranean climate even
at a decennial scale.
5. Conclusions
Our high-resolution geochemical study of sapropel S1 from the
Cretan Ridge (Eastern Mediterranean) shows that:
1) The top of the original sapropel was affected by post-depositional
alteration by a downward penetrating oxidation front, resulting in
the removal of organic matter. The ultra high-resolution µ-XRF
elemental analysis reveals a more articulated Mn/Al profile than
expected, with the development of a multiple peak pattern. This
peculiar profile may be explained by a “not constant” upward
migration of dissolved Fe and Mn and/or by a non-constant
downward diffusion of bottom water oxygen, probably linked to
rapid variations in the sedimentation rate.
2) The Corg/Porg ratio is in agreement with an enhanced regeneration
of phosphorus in respect to C caused by low low-oxygen content of
bottom waters and sediments (Ingall and Jahnke, 1994) during
sapropel deposition (Slomp et al., 2002).
3) Though aware of a possible analytical bias, we consider detrital
phosphorus as a reliable indicator of detrital supply from the
continent. In this case, its increase supports the hypothesis of an
enhanced detrital input during sapropel S1 deposition.
4) The very high-resolution proxy record obtained by XRF analysis
allowed us to perform a spectral analysis. High-frequency
millennial to decennial-scale solar cycles centered at 1700, 550,
210, 85–70, 60 and 50 years were identified, suggesting that also
during sapropel S1 deposition, climate in the Mediterranean region
was paced by solar variability even at short periodicities. Our
approach suggests that the use of µ-XRF scanning technique is a
powerful tool that can be used in order to obtain high high-
resolution records suitable for the identification of meaningful
periodicities.
Acknowledgements
We warmly thank Cesare Corselli and Daniela Basso for providing
the core material, Thierry Adatte for the Rock-Eval analyses and Kurt
Barmettler for ICP-OES measurements. We also thank Phil Meyers and
two anonymous reviewers for their useful revision of the manuscript.
This research is funded by the Swiss National Foundation (Ref.
200021-111694).
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Role of sea-level forced sedimentary processes on the distribution of organic

carbon-rich marine sediments: A review of the Late Quaternary sapropels in the
Mediterranean Sea
Rossella Capozzi a,⁎, Alessandra Negri b
a
Dipartimento di Scienze della Terra e Geologico-Ambientali, University of Bologna, Via Zamboni 67, I-40126 Bologna, Italy
b
Dipartimento di Scienze del Mare, Polytechnic University of Marche, Via Brecce Bianche, I-60131 Ancona, Italy

A R T I C L E I N F O A B S T R A C T

Article history: The 124 ka to present sapropel S5–S1 series in the eastern Mediterranean Sea, correspond to the last Glacial–
Received 3 December 2007 Interglacial period, and permit detailed investigation of 5th order sedimentary frequencies. The Sapropel
Received in revised form 5 May 2008 layers are clustered in high-frequency Milankovian cycle that occur within sequence stratigraphic 4th order
Accepted 6 May 2008
cycles of late Pleistocene-Holocene sea-level oscillations. The sea-level changes had an amplitude exceeding
120 m and have been correlated to the glacial-interglacial cycles modulated by the 100 ka eccentricity. Using
Keywords:
Sapropel
published data we examined occurrences of the complete S5–S1 series in the Mediterranean Sea and then we
Sea level focussed on two stratigraphic sequences in the central Adriatic shelf and Middle Adriatic Depression where
Sequence stratigraphy sapropels S5 and S1 were deposited during periods of sea-level rise recorded by the Transgressive Systems
Productivity Tract (Marine Isotopic Stage 5 and 1, respectively). Sapropels S4 and S3 were deposited during the Highstand
Mediterranean Sea Systems Tract, that developed throughout MIS 5 of the late Pleistocene sequence. Sapropel S2 should have
been deposited during the warm MIS 3.3 and followed the MIS 4 sea-level drop when sediment supply was
enhanced during the late highstand and falling stage of sea-level of the late Pleistocene sequence. The
pronounced MIS 2 cold stage led to a lowstand and to the regional erosional surface (Sequence Boundary).
We also compared the Adriatic sapropel S5–S2 sequence (4th order) to the Mid-Pliocene cluster “O” sequence
(3rd order). In both cases, sapropels are well formed before the increase of sediment supply due to
progradation of the shelf wedge, that occurs in the late high stand and initial falling stage in sea-level. Finally,
we considered the influence of sea-level lowering which could cause a weakening of North Adriatic Deep
Water formation, therefore influencing the Mediterranean deep water circulation. This condition would
favour oxygen depletion, but it does not correspond to a well developed sapropel (as in the case of S2). Based
on the assumption that productivity increases related to insolation play a dominant role in their
sedimentation, sapropel S2 is the result of low amplitude insolation maxima, that were unable to generate
a productivity increase leading to the burial of conspicuous amount of organic matter. Therefore, in the
Adriatic Sea the absence of the S2 sapropel is correlated to the high sedimentation rate diluting the signal,
whereas in the eastern Mediterranean basin this sapropel is virtually absent because of a weak orbital forcing
combined with oxidation that erased its record.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction explain their mode of sedimentation. Initial ideas invoked stagnation

Sapropels are dark, organic matter rich, often laminated sediments
that have cyclically been deposited in the Mediterranean area starting
from the late Miocene. The study of these sediments has been the
subject of debate during the last 50 years and the literature regarding
the argument is very abundant (see Negri et al., this volume).
Sapropels were defined by Kidd et al. (1978) as well-delimited
layers within open marine sediments, with thickness N1 cm and
organic carbon content N2%. Two models have been forwarded to
⁎ Corresponding author. Fax: +39 0512094522.
E-mail address: rossella.capozzi@unibo.it (R. Capozzi).
as the principal cause (e.g., Olausson, 1961; Cita et al., 1977; Vergnaud-
Grazzini et al., 1977; Thunell and Williams, 1989; Aksu et al., 1995).
However, other authors considered enhanced primary production in
the photic zone to be primary among the factors controlling the
concentration and accumulation of organic matter in the sea floor, and
hence the major cause of sapropel deposition (Calvert, 1983; Pedersen
and Calvert, 1990 among others).
More recently, a general agreement has emerged that sapropel
deposition is accompanied by conditions of anoxia or dysoxia (e.g.
Emeis et al., 1996; Cramp and O’Sullivan, 1999) and that the recurrence
of these layers is related to the Milankovitch precessional cycles
(Hilgen, 1991), favouring a combination of productivity and stagnation

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.05.009
250 R. Capozzi, A. Negri / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257
(e.g. Rohling and Gieskes, 1989; Rohling, 1994; Emeis et al., 2000a,b;
Warning and Brumsack, 2000). Although both factors have evolved from
the Pliocene to Pleistocene (Passier et al.,1999; Martinez-Ruiz et al., 2003)
sapropel formation in the eastern Mediterranean is evidently related to
variations in the intensity of the African monsoon. During Earth axis
precession minima, corresponding to maximum summer insolation in
the northern hemisphere, the increased monsoonal precipitation over
northern Africa enhanced runoff to the Mediterranean Sea (e.g.,
Rossignol- Strick, 1983, 1985, 1999; Rossignol-Strick et al., 1982). The
increased fresh water input lowered the salinity of the surface waters
causing the slow down or arrest of thermohaline ventilation in the deeper
parts of the Mediterranean and leading to anoxic bottom water. At the
same time, the increased runoff combined with a shallowing of the
nutricline into the photic zone led to enhanced primary productivity and
therefore an increased export of organic material to the sea floor (Rohling
and Gieskes, 1989; Rohling, 1991; Corselli et al., 2002).
The extensive literature regarding sapropels is mainly based on
studies regarding micropaleontological and geochemical aspects,
whereas studies of the sedimentological aspect are generally rare
(cf. Sigl et al. 1978; Stow et al. 2001; Hassold et al., 2003). Furthermore,
very little is known about the possible effect of sea-level variations on
sapropel deposition. The sapropels that formed during times of low
sea-level stand are especially interesting as the low sea-level at these
times likely restricted circulation and exchange through the Gibraltar
and Sicily straits (Zahn et al., 1987) and also drastically reduced the
size of the Adriatic Sea, known today as a source of major formation of
Eastern Mediterranean deep water.
Literature dealing with the role of sea-level variations on
deposition of Cenozoic sapropels is not abundant and so far limited
to the Middle Pliocene (Capozzi and Picotti, 2003; Roveri and Taviani,
2003; Marsaglia et al., 2004; Capozzi et al., 2006), whereas it is more
abundant for older successions, generally due to the fact that Paleozoic
and Mesozoic black shales are objects of hydrocarbon exploration.
A few papers have documented that some Neogene sapropels,
Cretaceous OAEs and older black shales occurred during trangressions
and high sea-level (Wignall, 1994; Stefani 2002; Capozzi and Picotti
2003; Arthur and Sageman 2005; Beckmann et al. 2005), whereas
others sequences have been correlated to low stands in sea-level
(Cobianchi and Picotti, 2001; Henz and Zeng, 2003).
According to the conceptual model by Huc (1988), organic matter
accumulation results from the combination of several favoring factors
that are, first of all, high primary productivity (Pedersen and Calvert
1990) and enhanced preservational conditions. The accumulation is
modulated by other factors intrinsic to sedimentation rate, such as
dilution, time of residence of the organics at the sediment surface,
water depth, detrital or biogenic mineral phases and distance from the
shore (Stow et al., 2001).
From this conceptual model, the aim of our paper is to assess the
role of sea-level variations in modulating the depositional record in
the different physiographic basin settings (platform, slope, abyssal
plain) that characterize siliciclastic systems, since these systems react
to sea-level oscillation by changing the balance between the rate of
sediment supply and the rate of creation of accommodation space.
The sequence stratigraphic approach (sensu Van Wagoner et al.,
1990) to study organic carbon-rich sedimentary intervals (sapropels and
black shales) documents their main occurrence within condensed
sections that correspond to maximum flooding surfaces (Vail et al.,1984;
Posamentier and Allen, 1999), or during the subsequent period of high
sea-level, within 3rd-order cycles. Generally, the organic matter that
accumulates under these conditions, has a marine origin (Type II
kerogen, e.g. Klemme and Ulmisheck, 1991). On the other hand, very
important petroleum systems pertain to sediment sequences inter-
preted as beeing deposited during periods of low sea-level (Henz and
Zeng, 2003). In these cases accumulation of organic carbon-rich layers
mainly shows a high percentage of kerogen type III that is related to an
increase of terrigenous supply (Klemme and Ulmisheck, 1991).
Relation between sea-level oscillations and the Corg-rich levels
have been described mainly in third order sequences (1–3 My
according to Vail et al., 1977; Posamentier et al., 1988). Within these
sequences each Systems Tract, which is constituted by genetically
associated stratigraphic units that were deposited during specific
phases of the relative sea-level cycle (Posamentier et al., 1988), can
include higher frequency cycles (fourth order: 0.1–1 My; 5th order:
0.01–0.1 My; Mitchum and Van Wagoner, 1991) that correspond to the
Milankovian orbital perturbations. The climatic oscillations that
generate the sapropels are related to eccentricity, obliquity and
precession and therefore corresponds to cycles of 4th and 5th order
(Mitchum and Van Wagoner, 1991). Therefore, for a detailed study of
the relation between the sedimentary record and deposition of the
Corg-rich levels we must focus attention on those sedimentary
successions in which these cycles are well developed. This situation
happens especially in the late Pleistocene, where large amplitude
glacial-interglacial oscillations of sea-level generate complete 4th
order sequences (Vail et al., 1977; Mitchum and Van Wagoner, 1991).
2. Sapropel record in the Mediterranean sea
We focussed on a short stratigraphic interval between Marine
Isotopic Stages (MIS) 5 and 1, which corresponds to the last 124 ka. In
the Mediterranean Sea this interval records two large sea-level
oscillations (over 120 m) and a continuous sedimentary record.
The synchronous occurrence of sapropels within different deposi-
tional systems and from various physiographic settings is useful to
understand the most favourable conditions for their record in the
sedimentary succession. With this purpose, we made an inventory of all
the sites in the Mediterranean basin, where a continuous sedimentary
succession of the last 124 ka occurs and the complete series from
sapropel S1 to sapropel S5 is available.
Table 1 summarizes for each location (ODP sites, DSDP sites and
other published data, see Fig. 1) the presence of the “Brunhes”
sapropels (Cita et al., 1977) and/or the occurrence of other horizons
not clearly labelled.
In the Western Mediterranean and in the Tyrrhenian Sea the
“Brunhes” sapropels do not occur (Table 1) although, Murat (1999)
recognized some minor organic carbon-rich horizons in the Alboran
Sea, their occurrences are in the last interglacial and do not
correspond to the S1 sapropels found in the Eastern Mediterranean.
In the Eastern Mediterranean Basin (Fig. 1, Table 1), occurrences of
the “Brunhes” sapropel (Cita et al., 1977) are widespread, although the
series are sometimes locally incomplete. In particular, concentrating
on the last two interglacials, the most recognizable horizons are S5
and S1, whereas sapropel S2 was recognized only in cores RC9-181,
ODP 967, M40/1-22 (Vergnaud-Grazzini et al., 1977; Emeis et al., 1996;
Löwemark et al., 2006); in addition, S3 and S4 do not appear in some
locations. An important recent finding of an almost complete sapropel
series in shallow waters comes from the Adriatic Sea, where core
Prad1-2 in approximately 70 m of sediments contains the last 370 ka
(Piva et al., 2008a,b) and the series of sapropels S1 to S10 except for S2.
Because our data compilation (Table 1 and Fig. 1) shows that the
complete series of “Brunhes” sapropels is mostly recorded in the
deeper sites (bathyal plain) of the basin but it is present in slopes and
shelves as well (Table 1), two questions arise: 1) what are the factors
that allow the presence of sapropels in the sediment record? 2) Does
the sapropel record depend on a low sedimentation rate and/or on a
different preservation potential?
An interesting paper by Murat and Got (2000) examines the TOC
content in sapropel S1 occurrences to show that a positive correlation
exists between TOC concentration and depth and that, regardless of
location or setting, the same percentage of organic carbon is
preserved at the same depth. As a consequence, the greater is the
organic carbon content the greater is the possibility to preserve the
sapropel record.
 R. Capozzi, A. Negri / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257 251

Table 1
Core data set used for this work

Lat. Long. Depth Thickness References

Western Mediterranean sites
ODP 650 Thyrrenian Sea Marsili Basin 39°21,40'N 13°54,05'E 3516.30 633.80 NO Kastens, Mascle et al., 1987.
ODP 651 Thyrrenian Vavilov Basin 40°09,03'N 12°45,39'E 3578.00 550.90 NO Kastens, Mascle et al., 1987.
ODP 652 Thyrrenian Sardinia continental 40°21,30'N 12°08,59'E 3446.00 721.10 NO BRUNHES SAPROPELS Kastens, Mascle et al., 1987.
Margin
ODP 653 Thyrrenian Cornaglia Terrace 40°15,86'N 11°26,98'N 2817.00 240.70 NO EVIDENT SAPROPEL Kastens, Mascle et al., 1987.
ODP 654 Thyrrenian Sardinia continental 40°34,76'N 10°41,80'E 2208.00 483.40 first sapropel 44 m depth Kastens, Mascle et al., 1987.
Margin
ODP 655 Thyrrhenian rise in the Vavilov basin 40°10,33'N 12°27,92'E 3290.00 90.40 First sapropel 8 m depth Kastens, Mascle et al., 1987.
ODP 656 Thyrrhenian Sea Monte de Marchi 40°11,96'N 12°11,03'E 3597.00 236.40 NO Kastens, Mascle et al., 1987.
ODP 963 Sicily Channel 37°01,938'N 13°10,896'E 481.00 199.40 NO Kastens, Mascle et al., 1987.
ODP 972 Ionian Sea Western Mediterranean 35°46,797'N 18°43,515'E 3942.00 95.40 NO Comas, Zahn et al., 1996.
Ridge
ODP 974 Thyrrhenian Sardinia Continental 40°21,364'N 12°08,506'E 3458.80 204.50 First sapropel 22 m depth Comas, Zahn et al., 1996.
Margin = ODP site 652
ODP 975 Balearic Sea Basin NW Flank 38°53,795'N 4°30,587'E 2427.60 317.10 First sapropel 3.8 m depth Comas, Zahn et al., 1996.
ODP 976 Alboran Basement Ridge 36°12,318'N 4°18,800'W 1107.50 928.70 NO SAPROPEL but continuous Comas, Zahn et al., 1996.
succession MIS 1–5 Cita et al. (1977), Capotondi
and Vigliotti, 1999,
von Grafenstein et al., 1999)
ODP 977 Alboran Basin 36°01,907'N 1°57,319'W 1995.50 598.50 first sapropel 2.0 m depth Comas, Zahn et al., 1996.
ODP 978 Alboran Basin 36°13,867'N 2°03,424'W 1941.00 698.00 NO Comas, Zahn et al., 1996.
ODP 979 Alboran Basement Ridge 35°43,427'N 3°12,353'W 1074.00 580.90 NO Comas, Zahn et al., 1996.
KET 8022 Thyrrhenian Sea 40°35,00 N 11°42,50' E 2430.00 No sapropel but all MIS (1–5) Paterne et al., 1986, 1988

Eastern Mediterranean complete succession

PRAD1-2 Adriatic Sea 42°40'34,7826qN 14°46'13,5565qE 185.50 71.20 S1, S3, S4, S5, S6, S7, S8, S9, S10 Piva et al., 2008a,b
KC01B Ionian Calabrian Ridge 36°15,25'N 17°44,34E 3643.00 S1, S3, S4, S5, S6, S7, S8, S9, S10 Sanvoisin et al., 1993;
Castradori, 1993
BD2002-GC01 Calabrian Rise 37°33.89671’N 17°48.32200’E 2470 3.41 S1, S3,S4,S5 Giunta et al. 2006
M25/4-13 Ionian slope 37°33.21'N 17°49.44' E 2533.00 16.30 S1, S3, S4, S5, S6, S7, S8, S9, S10 Schmiedl et al., 1998
M25/4-12 Ionian slope 37°57.98′N 18°11.04′E 2468.00 15.60 S1, S3, S4, S5, S6, S7, S8, S9, S10 Negri et al., 1999
D03 PC Mediterranean Ridge 34°53.16′N 20°48.54′E 2825.00 8.40 S1, S3, S4, S5 (2m), S6, S7, S8 Fusi et al., 1996
M40/1-22 Olimpi area 33°39.5′N, 24°41.2′E, 2004.00 7.00 S1, S2, S3, S4, S5 , S6, S7, S8, S9, Lowemark et al., 2006
S10
971 A Levantine Sea Napoli Volcano 33°42,190'N 24°42,814'E 2037.50 203.50 S1, S3?, S4?, S5?S6?, S7?, S8? Emeis, Robertson et al., 1996
RC9-181 South Crete Levantine basin 33°25,00'N 25°01,00E 2286.00 S1, S2, S3, S4, S5 , S6, S7, S8, Cita et al., 1977, Vergnaud-
(hiatus S3) Grazzini et al., 1977
KL51 ESE Crete 34°48.83’N 27°17.77’E 2158.00 7.00 S1, S3, S4, S5 , S6, S7, Frydas and Hemleben 2007
967 Levantino Base N flank Eratostene 34°04,098'N 32°43,523'E 2564.20 600.30 S1, S2, S3 , S4, S5 S6?, very Emeis, Robertson et al., 1996
bioturbated

Eastern Mediterranean missing S3 or S4 or both

SIN97-GC05 Medina Rise 34° 55’38”N 17°04’04”E 1075 4.52 S5, S6, S7, S8 Giunta et al., 2006
ODP 964 Ionian Calabrian Ridge 36°15,623'N 17°44,990'E 3668.00 101.80 S1, S5 Emeis, Robertson et al., 1996
ODP 973 Ionian Western Mediterranean 35°46,820'N 18°56,889'E 3706.50 148.50 S1, S?, S5, S6, S7? Emeis, Robertson et al., 1996
Ridge
M40/1-10 Mediterranean Ridge 34°45.8′N 19°45.7′E 2972.00 8.3 S1, S5 , S6, S7, S8, (hiatus S3) Lowemark et al., 2006
D05 PC Mediterranean Ridge 34° 52.64′N 20° 48.80′E 2817.00 5.38 S1, S4, S5, S6, Fusi et al., 1996
D04 PC Mediterranean Ridge 34° 52.80′N 20°51.27′E 2680.00 8.26 S1,S?, S5, Fusi et al., 1996
D10 PC Mediterranean Ridge 34° 52.78′N 20°46.78′E 2671.00 5.66 S1, S?, S6, S8 Paterne et al., 1986, 1988
U08 GC Mediterranean Ridge 34° 59'26.40′N 21°01' 08.09qE 2150.00 5.88 S1, S4, S5, S6, S7 Fusi et al., 1996
UM94PC17 Urania basin Area 35°13’56.4”N 21°24’42.6”E 3224 5.00 S1,S5,S6 Giunta et al., 2006
U01 GC Mediterranean Ridge 35°11'48qN, 21°24' 45qE 3227.00 3.75 S1, S5, S6, S7, S8 Fusi et al., 1996
SIN97-GC01 SW Crete 35° 07’27’’N 22°42’02.31”E 933 3.08 S1, S4,S5 Giunta et al., 2006
BAN84-GC27 Katia basin 33° 20.99’N 23°13.26’E 2026 4.96 S1, S5, S6,S7, S8, S9 Giunta et al., 2006
U06 PC Mediterranean Ridge 35°07'15,21qN 24°15' 05.43′E 2582.00 4.72 S1, S4, S5, S6, S7, S8 Fusi et al., 1996
BAN88-GC11 Area Prometheus 2 33° 49.10’N 24°26’E 1910 5.62 S1, S4,S5, S6,S7,S8 EEMIANO Project

Eastern Mediterranean uncertainty in missing sapropels

BAN89-GC09 Napoli dome 33° 37.98’N 24°43.29’E 2011 3.27 S1, S4,S5 Giunta et al., 2006
ODP 969 Levantine-Mediterranean Ridge 33°50,399'N 24°53,066'E 2211.80 108.30 S1,S3,S5, S6,S7,S8 Emeis, Robertson et al., 1996
BAN82-GC16 Erodothus Abyssal Plain 32° 34.42’N 26°50.85’E 3008 4.47 S1,S5,S6, S8 Giunta et al., 2006
ODP 966 Levantine Eratostene Top 33°47,799'N 32°42,095'E 937.70 106.80 S1, S5? S6, S?, S? Emeis, Robertson et al., 1996
ODP 965 Levantine Eratostene Northern flank 33°55,080'N 32°42,785'E 1517.70 250.40 Only S1 Emeis, Robertson et al., 1996
ODP 970 Levantino Volcano Milano 33°44,194'N 24°48,120'E 2086.90 201.40 Only S1(short core) Emeis, Robertson et al., 1996

An important factor that can affect the sapropel record is top-down
oxidation as reported by Löwemark et al. (2006). In fact, the so called
sapropel burn-down is a process implying that sapropels can be
partially and sometimes completely oxidized. Löwemark et al. (2006)
show that all sapropels from S1 to S11 experienced variable top-down
oxidation and that none of them maintained their original thickness.
This work indicates that the original thickness and TOC concentration
influence the burn-down rate and that local and regional setting, in
relation to deep water circulation, plays a major role in the
preservation of sapropels even if variations in the sedimentation
rate are evident. In particular, cores collected far from well oxygenated
watermasses generally display better preserved sapropels.
252 R. Capozzi, A. Negri / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257

Fig. 1. Eastern Mediterranean Sea map showing the location of the cores listed in Table 1. Black stars refer to cores in which a complete sapropel S5 to S1 series has been described.
White circles refer to cores where the sapropels S5 to S1 series is not complete. The white cross shows the location of Chirp sonar AMC 237 and AMC 178 (see Ridente and Trincardi
2002 and 2005 for details).

Finally, an important conclusion of Löwemark et al. (2006) is that part of this latter interval, spanning from about 35 ka to 8 ka, record
the best preserved sapropels exist when a succession of clustered the sea-level fall that continued until about 12 ka (Ridente and
strong insolation maxima occurred. In contrast, moderate or weak Trincardi, 2005). In Table 2 we report the values that we obtained from
insolation maxima followed by weak insolation maxima are asso- three cores, each representative of a different depositional condition
ciated with the poorest preserved sapropels, often only detectable as (shelf, lower slope, bathyal plain). Major findings are: 1) the mean
“ghost” sapropels through geochemical analysis. sedimentation rate in the bathyal plain and in the lower slope remains
Therefore, the data suggest that although sapropels were depos- in the same order of magnitude, even if it decreases during the interval
ited throughout the eastern Mediterranean and Adriatic sea, their Y5-S1. This lower sedimentation rate can couple with African dryer
sedimentary record can be affected by strong burn-down effects. climate during which the entire Nile system must have been reduced
to intermittent seasonal flow (Lamb et al., 2007 cum bibl.); 2) the
3. Stratigraphic and sedimentary framework sedimentation rate between S5 and Y5 on the Adriatic shelf is one
order of magnitude higher than at deeper locations and, between Y5
In order to highlight possible variations in sediment supply and and S1 a further increase of terrigenous supply was directly linked to
their relations with variations in sea-level during the studied time the sea-level fall and the developing forced-regressive wedge.
interval, we examined published data and calculated sedimentation The sedimentary sequence on the shelf is, obviously, the most
rates in different depositional systems, such as shelf, slope and bathyal appropriate to obtain information on the relation between the relative
plain (Table 2). We used as an age marker the Y5 tephra (Keller et al., position of sea-level and the deposition of sapropelic intervals. In fact,
1978; Emeis et al., 1996), which is the closest layer to the Last Glacial this depositional system is directly influenced by variations of the
Maximum (LGM). We calculated the average sedimentation rate terrigenous supply induced by sea-level oscillations. For this reason,
between insolation-cycle 12 (S5 - Hilgen, 1991)) and Y5. Then, we we referred to the abundant literature regarding the Adriatic Sea in
calculated the average sedimentation rate between Y5 and the order to locate the position of different sapropels within the
subsequent transgression up to insolation-cycle 2 (S1). The main sedimentary sequences occurring in this area. In particular, according
to Ridente and Trincardi (2005, cum bibl.), the upper Pleistocene–
Holocene stratigraphic succession of the central portion of the western
Table 2
Sedimentation rate in the eastern Mediterranean and Adriatic sea calculated using S1, Adriatic margin records relative sea-level variations related to ca.
S5 and Y5 data point (see text) 100 ka glacio-eustatic cycles. Following the Last Glacial Maximum and
until ca. 6 ka BP, sea-level rose about 125 m, or up to 149 m (Lambeck et
Core Location Depth S1–Y5 sed. rate Y5–S5 sed. rate
(mm/year) (mm/year) al., 2004; Antonioli and Vai, 2004) from its lowstand position to the
967 Levantino Base 2564.20 0.024 0.070
modern highstand (Fairbanks, 1989; Bard et al., 1996). According to
N flank Eratostene Ridente and Trincardi (2005), four depositional sequences (numbered
973 Ionian Western 3706.50 0.012 0.043 1 to 4, topdown) bounded by regional erosional unconformities and
Mediterranean Ridge their distal conformities (namely ES1 to ES5) record cycles older than
PRAD1-2 Adriatic Sea 185.50 0.38 0.200
the Holocene (between ca. 25 and 450 ka). The four Pleistocene
 R. Capozzi, A. Negri / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257 253

depositional sequences appear internally composed of laterally
continuous forced-regressive units, extending from the western flank
of the Middle Adriatic Depression (MAD) to the area south of the
Gargano Promontory. The uppermost forced-regressive unit (sequence
1 of Ridente and Trincardi, 2005) is the result of the Po delta
progradation and is younger than 30–35 ka (Ridente and Trincardi
2005) based upon the presence of the Y5 “Campanian Ignimbrite”
tephra layer (35 ka n.c. age, Calanchi et al., 1996, 1998) close to its base.
Dating of the sequences based on the analysis of several cores
(Trincardi et al., 1996; Asioli, 1996) allows reference of erosional
surface ES1, which truncates sequence 1, to the sea-level fall and
lowstand of the Last Glacial Maximum (Oxygen Isotope Stage 2, ca. 20–
30 ka) and identifies deposits from Stages 4 and 5 within the lower part
of sequence 1 (Ridente and Trincardi 2005). The underlying erosional
surface ES2 was indirectly referenced to the lowstand of Isotope Stage
6 (ca. 130–140 ka, after Martinson et al., 1987; Ridente and Trincardi,
2005).
Above the ES1 sequence boundary, the late Pleistocene–Holocene
Trangressive Systems Tract (TST) and the late Holocene Highstand
Systems Tract (HST) show shore-parallel depocentres (Cattaneo and
Trincardi, 1999; Correggiari et al., 2001), likely suggesting advection of
fine-grained sediment as the shelf was progressively drowned during
the sea-level rise (Cattaneo and Trincardi, 1999). Muddy deposits,
more than 30 m thick (Ciabatti et al., 1987), characterize the highstand
interval that accumulated on the shelf during the last ca. 6 ka
(Holocene HST, Correggiari et al., 2001; Cattaneo et al., 2003).
In the chronostratigraphic chart of Fig. 2 the systems tracts have been
drawn by correlation between sea-level position (after Waelbroeck et al.,
2002) and the geometry and distribution of the seismic facies in the
central portion of the western Adriatic margin (cfr Fig. 3, Ridente and
Trincardi, 2002). Sapropels S5 to S1 have been located on the
chronostratigraphic chart based on correlation with the sea-level
curve and Marine Isotopic Stages (Löwemark et al. 2006; Martinson
et al.,1987). It can be observed that sapropels S5 and S1 are located in the
same depositional context (TST), whereas sapropels S4, S3 and S2 fall
within sequence 1 at different stratigraphic levels, within the Highstand
Systems Tract or, in the case of S2, within the Falling-stage Systems Tract
(FST). Sapropels S4, S3 and S2, in Fig. 2, also correlates with the TST of a
5th-order sequence within a HST and an FST of a 4th-order sequence.
In addition, we examined two acoustic Chirp sonar profiles: AMC 237
(Ridente and Trincardi 2005), located south east of the MAD, oriented
SW-NE, and AMC 178 (Ridente and Trincardi, 2002) located north of the
Gargano promontory and oriented SE-NW that are representative of the
sedimentary record (Ridente and Trincardi, 2002).
On the line-drawing of these profiles (Fig. 3) we located the ES1
and ES2 sequence boundaries (as indicated by Ridente and Trincardi,
2002, 2005) and the geometry of the major reflectors.
According to Fig. 2, therefore, sapropel S5, on the deeper north-
eastern part of the profile AMC 237, should be located in the lower part of
Sequence 1, within a plane-parallel unit that represents an aggradational
phase of deposition that Ridente and Trincardi interpreted as the TST. S4
and S3, in contrast, should occur in the upper part of the sequence,
which shows low-dipping-angles oblique clinoforms. Ridente and
Trincardi (2002) suggest that this geometry records a condition of
enhanced sediment supply on the inner shelf during the late highstand
and early falling of sea-level. In the AMC 178 the HST is well developed
and the overlying unit shows higher dipping angles and evident
downlap terminations, linked to the deposition of the regressive
wedge during the subsequent sea-level fall (Ridente and Trincardi,
2002). As the base of the distal forced-regressive wedge is dated to after

Fig. 2. Chronostratigraphic chart which displays both the horizontal distribution of the component sedimentary layers of the studied sequences and the significant hiatuses in
sedimentation. The systems tracts have been drawn by means of the correlation between the sea level position (after Waelbroeck et al., 2002) and the geometry and distribution of
the seismic facies in the central portion of the western Adriatic margin (cfr Fig. 3 Ridente and Trincardi, 2002). The position of sapropels S5 to S1 has been reported on the
chronostratigraphic scheme after the correlation of their occurrence with respect to the sea level curve and Marine Isotopic Stages (Löwemark et al 2006; Martinson et al., 1987).
254 R. Capozzi, A. Negri / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257

Fig. 3. Line drawing of Chirp sonar AMC 237 and AMC 178 (see Ridente and Trincardi 2005 and 2002 for details). Definition of the different system tracts derives from the geometry of
the seismic reflectors according to Ridente and Trincardi (2002, 2005)) see text for further explanation.

30–35 ka, this means that in this sequence we should also observe
sapropel S2 (55 ka). Its occurrence, however, falls within the well-
developed prograding clinoforms, linked to enhanced sediment supply
during the late highstand and falling stage of sea-level. For this reason
terrigenous sediment supply likely prevented formation of an S2 Corg-
rich horizon in this framework.
Above the ES1 sequence boundary, the Holocene succession shows a
plane-parallel geometry of the seismic reflectors. The Holocene mud
deposits can be divided into a lower unit TST, which includes the S1
horizon, and an overlying HST the base of which, according to Trincardi
et al. (1996) and Cattaneo and Trincardi (1999), is dated at 5.5 ka in the
studied region. Therefore, in the Holocene sequence the stratigraphic
position of S1 is equivalent to that of S5 in the underlying sequence 1,
showing the same depositional context as most sapropels and black
shales described in the literature. According to Van Wagoner et al. (1988,
1990), successive parasequences are built as sea-level rises, generating a
retrogradational stacking pattern (TST). As sea-level reaches highstand
conditions, the shelf is under fairly deep water and is starved for
sediment. A condensed section, a thin marine muddy interval,
characterized by very low depositional rate, is deposited. This
condensed interval commonly includes OC-rich layers composed of
mostly pelagic and hemipelagic clastics that are widely distributed
throughout the basin (e.g. Vail et al., 1984; Wignall, 1994). At this time,
pelagic sedimentation is less affected by clastics and is more sensitive to
the paleoceanographic setting, allowing a better recording of enhanced
primary productivity and/or density stratification in the water column.
Furthermore, under these conditions, the Particulate Organic Matter
(POM) settling velocity increases due to entrapment of pelites in marine
snow and to the production of large fecal pellets. This fact partially
prevents organic matter recycling in the water column, contributing to
sedimentation of a larger amount of organic carbon (Stow et al., 2001;
Bianchi et al., 2006). These processes proceed until the prograding shelf-
wedge during the HST (progradational stacking patterns of Van
Wagoner et al., 1990) overwhelm the marine organic carbon (OC)
input. At this latter time, OC-rich intervals can be deposited where low
sedimentation rates and muddy deposits persist up to the late HST. This
occurs in the slope, where hemipelagic deposition includes vertical
settling through the water column and slow lateral advection (Stow et
al., 2001) and in the basin plain, where pelagic settling is only
episodically interrupted by turbidity currents.
 R. Capozzi, A. Negri / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257
An example is provided by Capozzi et al. (2006) regarding
sapropels deposited during the Middle Pliocene HST (3rd-order
cycle) pertaining to the Cluster “O” (Verhallen, 1987; Lourens et al.,
1996). The Pliocene 3rd order cycle, spanning from 3.75 Ma to 2.87 Ma
(Capozzi and Picotti, 2003), records a sea-level drop (LST) and a
widespread turbiditic deposition, interpreted to be related to an
important glacial event in the Northern Hemisphere. After this event,
a climatic optimum (TST and early HST) from 3.3 to 3.042 Ma was
marked by the growth of a carbonate platform. A climatic deteriora-
tion, at the end of the warm Middle Pliocene between 3.042 and
2.87 Ma, occurred during a period of stable sea-level (late HST) and
caused the demise of the carbonate platform and the deposition of
sapropel cycles. These cycles record a constant sedimentation rate,
which indicates that variations in runoff and, consequently, in nutrient
supply, did not occur in the depositional system, whereas orbital
increases in the intensity of solar radiation were the main reason for
enhanced primary productivity. The deposition of these sapropel
layers occurred on the upper slope, where mud deposition continued
until a rapid fall in sea-level changed the sedimentary processes in
this location. This situation lasted about 140 ka during the Mid-
Pliocene, but it is easily comparable to the sedimentary conditions
described for S4 and S3. Furthermore, the deposition of the upper
Sapropel E (in Capozzi et al., 2006) may account for the sedimentary
conditions experienced during deposition of the S2 interval. In the
case of Sapropel E, in fact, the increase of sand supply not only strongly
diluted the marine organic carbon but also contributed terrestrial
organic carbon.
During sea-level fall, the shallower portions of the sea floor of epeiric
seas and the continental shelf are progressively exposed to subaerial
erosion. The erosion causes formation of the sequence boundaries, which
are diachronous and cap the previous HST, also eroding the surface of the
downstepping sediments, deposited during forced regression (FST) that is
associated with the sea-level fall (Catuneanu, 2002).
When lowstand is attained (LST), sediments transported down
valleys are delivered mainly off the shelf edge into deep water, to form
sea floor fans or lowstand wedges. Downslope resedimentation
processes, such as turbidity currents, debris flow and slides, are
dominant and the sedimentation rate increases in the basin plain.
These sediments can accumulate high amounts of organic carbon and its
rapid burial prevents its oxidation (Stow et al., 2001). In this lowstand
scenario, however, the occurrence of mainly gravity- and density-driven
sedimentary processes produce high-frequency oxygen replenishment
at the basin-floor and also cause dilution of primary-productivity
derived organic matter. Organic matter accumulation in sapropelic
layers can to some extent survive in the slope environment, where lutite
flow and cascading processes govern the deposition of fine-grained
sediment, during cyclic episodes of enhanced runoff.
Summarizing, the progradation of the shelf-wedge progressively
shifts sapropel deposition basin-ward that can be expressed from the
basin margin to the deep basin-plain only when terrigenous sediment
starvation is reached. During times of low sea-level, the slope and the
basin plain, if not reached by turbidity currents, are environments that
can better record enhanced organic carbon accumulation during
higher-frequency sea-level oscillations.
4. Sea-level control on watermass circulation
According to the data discussed in this paper, it is clear that
deposition of sapropels occurred under different sea-level conditions.
Whereas sapropels S5 and S1 were deposited during a rapid sea-level
rise, related to the deglacial phase, the others (S4, S3, S2) were deposited
during an interval recording sea-level still-stand and subsequent sea-
level fall.
According to the most recent models regarding sapropel S1
formation, increased fresh water input lowered the salinity of the
surface waters and stopped the formation of Deep Adriatic Water and, in
255
general, overall deep-water formation, causing a slow down or even
stoppage of thermohaline ventilation in the deeper parts of the
Mediterranean, favouring the formation of anoxic bottom water. At the
same time, the increased runoff combined with a shallowing of the
nutricline into the photic zone led to enhanced primary productivity and
therefore an increased export of organic material to the sea floor
(Rohling and Gieskes, 1989; Rohling, 1991, 1994, 2001; Corselli et al.,
2002). It is worth noting in this framework the modelling results
obtained by Bianchi et al. (2006), who pointed that sapropel S1
deposition occurred by the concomitant effects of absent reventilation
and enhanced productivity with the additional contribution of a large
POM sinking velocity.
This reconstruction fits also for the sapropel S5 which was deposited at
the beginning of an interglacial and therefore during a rapid sea-level rise
coupled with increased runoff. At times of deposition of sapropels S4 and
S3, the sea-level position, as reconstructed after Waelbroeck, 2002 (Fig. 2),
was −25 m lower than today, while sapropel S2 was deposited when the
sea-level was at least 50 m lower than today. The lowered sea-level means
that the northern Adriatic coastline was shifted few kilometres southward
during deposition of S3 and S4, and more that 100 km in the case of S2.
Cold, deep waters form in the Adriatic Sea during the winter in
response to heat loss to the atmosphere (Artegiani et al., 1989, 1997).
In particular, the North Adriatic Deep Water (NADW) is a water mass
formed in the north Adriatic Sea during strong “Bora” wind events.
The very dense deep water flows southward along isobaths near the
bottom of the Italian shelf. The flow partially sinks into the MAD, but
its major portion moves further southwards to reach the shelf off Bari,
where a canyon intersects the shelf and the water deepens. At this
point the NADW plays a role in the formation of Adriatic Bottom Water
(ABW) (see Artegiani et al., 1993).
During sedimentation of sapropel S2, extensive shelf areas had
emerged in the north of the basin, implying also a reduction in the size of
the water-mass subject to the “Bora” winds. According to the data shown
in Russo and Artegiani (1996), the lowest winter water temperatures are
reached in the northern Adriatic between the Northwestern coastline and
approximately the 20 m isobath. Therefore, it is probable that, at the time
of sapropel S2 formation, the NADW was weakened because large shelf
areas were exposed and as a consequence the formation of the ABW was
diminished. An implication of these factors is that the conditions for
sedimentation of sapropel S2 should have been facilitated because of the
slow down of thermohaline circulation and decreased ventilation at the
sea bottom. However, sapropel S2 is rarely found and its expression
corresponds to a not well expanded insolation maximum (Hilgen, 1991)
suggesting that the primary productivity did not increase sufficiently to
cause enough organic matter accumulation. This observation strengthen
the hypothesis that productivity played a major role in the formation of
sapropels and, for this reason, the S2 is a not well developed sapropel. This
situation makes the sapropel S2 more suitable for burn-down, and, as
demonstrated by Löwemark et al. (2006), the fate of sapropel S2 was to be
erased in many cases, eliminating its appearance in the vast majority of
the sediment record far collected at the sea bottom.
5. Conclusions
Sapropels levels S5 to S1, clustered in high frequency Milankovian
cycles, occur within a sequence stratigraphic framework consisting of
4th order cycles linked to late Pleistocene–Holocene sea-level
oscillations, which have amplitudes of over 120 m and have been
correlated to glacial-interglacial cycles modulated by the 100 ka
eccentricity.
1) In terms of sequence stratigraphic interpretation, sapropels S5 and
S1 in the central Adriatic shelf and MAD occur in the Transgressive
Systems Tract of two depositional sequences, that are assigned to MIS
5e and 1, respectively. Sapropels S4 and S3 are found within the HST
of late Pleistocene sequence 1 (Ridente and Trincardi, 2002, 2005),
256 R. Capozzi, A. Negri / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 249–257
which developed during MIS 5. Sapropel S2, in contrast, corresponds
to the warm MIS 3.3 and is part of the FST. It is noteworthy that S4, S3
and S2 were deposited during the TST of a 5th-order sequence within
a HST and an FST of a 4th-order sequence.
2) Sapropels S5 and S1 are widespread from the basin margins to the
plains of the Eastern Mediterranean. Under conditions of sea-level
rise, the sedimentary basin experienced starvation of terrigenous
sediments and therefore was more favourable to sapropel deposition.
Comparison of the S5 to S2 sapropel series with Mid-Pliocene
cluster “O” shows that, in both cases, sapropels may form until the
prograding shelf wedge of the late highstand and initial falling
stage in sea-level provides an increase in sediment supply, leading
to progressive dilution of marine organic carbon. This conditions
led to formation of sapropel S2 and the uppermost sapropel of
cluster “O” (Capozzi et al., 2006).
3) When lowstand conditions are attained, marine sedimentation
shifts off the shelf break, via mainly gravity-driven processes. In this
case, the increase in terrigenous supply in deeper areas may
contribute to storage of high amounts of organic carbon, although
dilution and mixing with terrestrial organic carbon commonly occur.
4) Low sea-level affects circulation in the Adriatic Sea and is likely
to cause a consequent weakening of formation of North Adriatic
Deep Water. This condition, which could prevent normal sea floor
ventilation, however, does not correspond to a well developed
sapropel S2. Productivity increases, paced by well developed
precession minima (insolation maxima), are suggested to play a
major role in sapropel deposition. Therefore, we suggest that
sapropel S2 is virtually missing in the eastern Mediterranean basin
because of a low amplitude insolation maximum, and consequent
insufficient productivity increase, combined with post-deposi-
tional oxidation that erased its record.
Acknowledgments
The authors are indebted to Giambattista Vai and Vincenzo Picotti
for critically reading the, first version of the manuscript. We warmly
thank Alessandro Amorosi and an anonymous reviewer whose
comments greatly help to improve the paper. RFO Funding to R.C. is
gratefully acknowledged.
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Benthic environmental changes in the Eastern Mediterranean Sea during

sapropel S5 deposition
Caterina Morigi ⁎
Dipartimento di Scienze del Mare, Università Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy

a r t i c l e i n f o a b s t r a c t

Article history: High resolution benthic foraminiferal analyses of sediment cores collected at different sites in the Eastern
Received 29 November 2007 Mediterranean Sea revealed that profound changes occurred in deep-sea ventilation over the past 124–119 ka
Received in revised form 16 October 2008 BP. The three cores (SIN97-GC01, BAN89-GC09, BD02-GC01) were selected in order to investigate middle and
Accepted 21 October 2008
deep bathyal ecosystems in the Eastern Mediterranean basin. At site SIN97-GC01 (933 m water depth, Urania
Basin), the presence of benthic fauna in the sapropel layer, and the gradual increase in benthic foraminiferal
Keywords:
Benthic foraminifera
abundance from the middle part of the sapropel, suggest that the sea-floor was partially ventilated and that
Oxygen concentration re-oxygenation had increased considerably during the late phase of S5 deposition. Cores BAN89-GC09
Sapropel (2011 m water depth, Napoli Dome) and BD02-GC01 (2470 m water depth, Ionian Sea) show a different
Mediterranean Sea pattern. During sapropel S5, benthic abundance and diversity strongly decrease and microfauna even
Eemian disappears in some levels, suggesting the establishment and maintenance of stagnant and anoxic conditions
at the seafloor until the end of S5 deposition. In the deepest part of the basin, the re-establishment of the
benthic foraminiferal community at the top of the S5 layer indicates a relatively slow bottom re-oxygenation.
At the southernmost site, the foraminiferal assemblage records a short oxygenation pulse during the
deposition of sapropel S5 linked to a short cold spell. The results of this study suggest that the evolution of
the dysoxic–anoxic conditions, as well as the re-oxygenation pattern at the end of the stagnant period, were
characterised by spatial and temporal variability, possibly controlled by basin physiography.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction Although benthic foraminiferal records yield important information,

Sapropels are dark organic-rich layers that were deposited
cyclically during the last 10 Myr in the Mediterranean Sea. Increasing
primary production, stratification of superficial waters, and sluggish
bottom-water ventilation are the mechanisms leading to the forma-
tion of these layers. Although several hypotheses have been proposed,
it is not yet well understood which of these mechanisms was most
important, or the precise way in which they led to anoxia in the
bottom waters. One of the best developed sapropel, termed S5, was
deposited during the last interglacial period (124–119 ka BP, see
stratigraphic framework paragraph for more details). Sapropel S5
formed during the insolation monsoon maximum of the last
interglacial period and was interrupted by a dry interlude of several
centuries, with corresponding cooling over the north of the
Mediterranean area (Rohling et al., 2002). This sapropel was
characterised by a high organic carbon and biogenic silica accumula-
tion rate and by the presence of laminations characterised by
diatomaceous laminae intercalated with thick layers of mineralogenic
detritus (Kemp et al., 1999; Corselli et al., 2002; Giunta et al., 2006).
⁎ Present address: Geological Survey of Denmark and Greenland (GEUS), Department
of Stratigraphy, Øster Voldgade 10, 1350 Copenhagen, Denmark. Tel.: +45 3814 2727.
E-mail addresses: c.morigi@univpm.it, cmor@geus.dk.
few papers deal with the assemblages of sapropel S5 (Parker, 1958;
Oggioni and Zandini, 1987; Nolet and Corliss, 1990; Vismara-Schilling
and Coulbourn, 1991; Schmiedl et al., 2003), and only those of Oggioni
and Zandini (1987) and Vismara-Schilling and Coulbourn (1991)
describe the finer fraction of the sediment (N63 µm). The benthic
faunal succession across sapropel S5 is summarised and re-inter-
preted by Jorissen (1999) who suggests that one of the factors
controlling benthic assemblages is the time between the onset of the
oxygen depletion and the re-oxygenation of the bottom environment.
The paleoceanography of the Eastern Mediterranean Sea during
the last interglacial cycle has been reconstructed from proxies such as
planktonic microfossils, organic biomarkers and oxygen and carbon
isotopes (Cane et al., 2002; Rohling et al., 2002, 2006; Capotondi et al.,
2006, Giunta et al., 2006; Sangiorgi et al., 2006; Marino et al., 2007). In
particular, water column dynamics were reconstructed using proxies
linked to the pelagic environment (Rohling et al., 2006; Marino et al.,
2007).
Results derived from planktonic microfossils (foraminifera, calcar-
eous nannofossils, diatoms and organic-walled dinoflagellate cysts)
and geochemistry of the same cores have been previously published
by Capotondi et al. (2006), Giunta et al. (2006) and Sangiorgi et al.
(2006) with the aims, respectively, to reconstruct a detailed strati-
graphic framework and to characterise the pelagic paleoecosystem

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.10.010
 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271
dynamics and the paleoceanographic evolution of the superficial
water masses during the sapropel S5.
The present study focuses on a high resolution analysis of the
distribution of benthic foraminifera across sapropel S5 from three
Eastern Mediterranean Sea cores. The main aim is to describe the
impact of short-term climatic and environmental changes on different
deep-sea ecosystems through the study of proxies related to the
benthic environment. With this goal in mind, three sites were selected
to investigate spatial and temporal variability during sapropel
deposition as recorded by the benthic microfauna.
1.1. Ecological significance of the benthic foraminifera microfauna
Few studies deal with the ecology of living benthic foraminifera in
the deepest part of the Eastern Mediterranean Sea (Parker, 1958; Cita
and Zocchi, 1978; Murray, 1991; De Rijk et al., 1999; De Rijk et al.,
2000; Pancotti et al., 2008). On the other hand, much has been learnt
in recent years about the ecology of deep-sea benthic foraminifera in
general and our knowledge of the ecological requirements of
important taxa has improved considerably (among others Gooday,
1988; Gooday and Rathburn, 1999; Schmiedl et al., 2000; Fontanier
et al., 2002, 2005; Shepherd et al., 2007; see also Gooday, 2003 and
Jorissen et al., 2007 for general reviews of foraminiferal ecology).
Furthermore, studies of the evolution of benthic foraminiferal
assemblages during sapropel deposition have increased our under-
standing of how these organisms respond to oxygen depletion
(Jorissen, 1999; Schmiedl et al., 2003). Information about the
ecological requirements of the species found in the present study is
summarised below. Genera and species are reported in alphabetical
order, with exception of selected groups.
Articulina tubulosa is not included with other miliolids (see below)
because it has a slightly different response to increased organic flux. In
modern sediments, it is considered to be an oligotrophic taxon (De
Rijk et al., 1999), limited to labile organic carbon flux regimes of b2.5 g
C m− 2 y− 1 (De Rijk et al., 2000). In post-sapropel deposits this species
occurs during the first phase of the re-oxygenation, when the deep-
sea environment is still food-enriched (Nolet and Corliss, 1990;
Jorissen, 1999).
Bolivina is normally considered a low oxygen tolerant taxon
(Bernhard, 1992) with a variable microhabitat. Some species are
epifaunal or shallow infaunal (e.g. B. spathulata), whereas other
species (e.g. B. dilatata) have a clear infaunal tendency (Barmawidjaja
et al., 1992; De Stigter et al., 1998). Although different species occupy
different microhabitats, all authors have linked these species to
eutrophic and low oxygen environments.
Cassidulina carinata depends on a relatively high flux of fresh,
highly nutritive organic matter (De Rijk et al., 2000) and occupies
dysoxic environments on the shelf (Hayward et al., 2007). In the
upwelling area off Mauritania, it dominates assemblages together
with Bolivina dilatata, Chilostomella oolina and Globobulimina affinis,
at stations where the organic flux is very elevated (N8 g/m2/year and
the bottom-water oxygen concentration is less than 3 ml/l (Morigi
et al., 2001).
Cassidulina crassa is common on the middle slope of the Adriatic
Sea, and has a shallow infaunal microhabitat (De Stigter et al., 1998).
This species is one of the dominant taxa in the size fraction 63–150 µm
of recent sediment samples from the 2800-m-deep lower canyon
station in the Bay of Biscay (Fontanier et al., 2005). Suhr and Pond
(2006) investigated the fatty acid composition of this species collected
off the Antarctic Peninsula, and reported that it responds rapidly to
the deposition of phytoplankton material from surface bloom events.
Very few studies deal with ecology of the genus Fissurina, probably
because of its small size and low abundance (e.g. 0.4% of the total
assemblage in the Bay of Biscay, Fontanier et al., 2005), as well as its
presence over a wide depth and geographical range. Living Parafis-
surina spp. were found in the abyssal zone of the Sulu Sea (4400 m
259
water depth) associated with nine other calcareous species (Szarek
et al., 2007). Gooday and Lambshead (1989) noted that Parafissurina
fusiformis typically inhabits phytodetritus aggregates in the Porcupine
Seabight (1345 m water depth). This species is also found in
association with G. subglobosa, E. exigua and A. weddellensis at abyssal
depths south of New Zealand in an area bathed by a cold, corrosive,
oligotrophic water mass (Hayward et al., 2007). Furthermore, Fissur-
ina spp. constitutes an important part of the recent benthic
microfauna on the hypohaline Black Sea shelf (Yanko, 1990).
Globocassidulina subglobosa is another widely distributed species
associated with phytodetritus (Gooday, 1993). Suhr et al. (2003)
reported that it plays an important role in the rapid cycling of
phytoplankton-derived organic carbon on the Antarctic Peninsula
shelf. In the Atlantic Ocean, G. subglobosa is most abundant in sandy
sediments and in areas with relatively strong bottom currents
(Mackensen et al., 1993, 1995; Schmiedl et al., 1997) and low
seasonality in surface primary production (Sun et al., 2006). Hayward
et al. (2007) found this species associated with a low flux of organic
matter to the seafloor in an oxic environment dominated by strong
currents.
Gyroidinoides spp. is a deep-water taxon, generally associated with
low-diversity assemblages related to low organic flux in recent
samples from the Mediterranean Sea (De Rijk et al., 1999).
A first group, lumped as miliolids, comprises large, thick-walled,
epifaunal genera (Pyrgo spp., Spiroloculina spp., Triloculina spp. and
Quinqueloculina spp.). These taxa inhabit well-oxygenated lower
bathyal and abyssal area of the modern Eastern Mediterranean Sea
and are adapted to a range of oligotrophic to mesotrophic environ-
ments (Kaiho, 1999; De Rijk et al., 1999; Geslin et al., 2004). Several
papers dealing with sapropel deposits indicate that this group is
characteristic of oligotrophic and well-oxygenated environments and
rapidly disappears when oxygen concentrations fall below critical
values (Jorissen, 1999; Kuhnt et al., 2007).
A second group, the phytodetritus taxa, consists of small rotaliids
that tend to have more or less opportunistic life styles. Normally, they
inhabit epifaunal or shallow infaunal microhabitats and occur in
relatively eutrophic (but not hypoxic) regions, although some species
(e.g. Epistominella exigua) can survive in oligotrophic settings (Gooday,
1988, 1993). These tiny species may reproduce rapidly in response to
strong pulses of fresh organic matter to the seafloor, as reported by
Gooday (1988) in the abyssal North Atlantic Ocean. They appear to
exploit phytodetritus when it accumulates on the seafloor after
phytoplankton blooms. Such species include Alabaminella weddellen-
sis, Anomalinoides minimus and Epistominella exigua (Gooday, 1988,
1993). Included in the same group based on their shell morphology
and occurrence in the same stratigraphic levels are Svratkina
tuberculata and other small rotaliids. However, there is no direct
evidence that these species respond to phytodetritus.
The third group comprises Globobulimina spp., Bulimina exilis,
Cassidulinoides bradyi, Chilostomella oolina, and Fursenkoina spp.
These taxa normally adopt a deep infaunal microhabitat, can survive
low oxygen conditions and feed on degraded organic matter at the
dysoxic–anoxic boundary. Several studies (see Fontanier et al., 2006
for a detailed bibliography) report that Globobulimina is a highly
specialised taxon that lives in a stable biogeochemical microhabitat.
Previous studies have suggested that members of this genus prefer
degraded rather than fresh organic material (Fontanier et al., 2002).
Nomaki et al. (2005, 2006) noted that Globobulimina affinis responds
relatively rapidly to fresh phytodetritus, and is able to ingest fresh
organic material, but can also consume sedimentary organic material
when fresh food is not available. A recent study (Risgaard-Petersen
et al., 2006) indicates that Globobulimina pseudospinescens, and
possibly other infaunal taxa, are able to respire nitrate, allowing
them to live in anoxic sediments for prolonged periods. Presumably,
the distribution of deep-infaunal taxa in anoxic sediments confers an
advantage in terms of food acquisition, predator avoidance, and/or
260 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271

Fig. 1. Bathymetric map of the Eastern Mediterranean Sea. Locations of the investigated cores are represented by dots. Also given are the locations of cores KS205, BAN81-30, BAN81-23,
ODP 971A, LC21, M40-4/67SL, and GeoTüKL83, (indicated by a star) which have yielded key results for comparison (see text and Table 1 for references).

reduced competition. Furthermore, when oxygen concentrations
decrease, epifaunal and shallow infauna benthic foraminifera dis-
appear, and the deep infaunal taxa migrate to the water-sediment
interface (Jorissen et al., 1995).
2. Materials and methods
The three cores were collected in different sub-basins of the
Eastern Mediterranean Sea (Fig. 1 and Table 1). The identification of
sapropel S5 in these cores was based on three main lines of evidence
(Fig. 2): 1) biostratigraphic analysis (Giunta et al., 2006) that allows
identification of the MNN21a Emiliana huxleyi zone (Rio et al., 1990);
2) when possible, the presence of the younger sapropels (S4 to S1) and
3) the dark colour of the sediment. For each core, the lower and upper
lithological limits of the sapropel are reported in Table 2.
Core SIN97-GC01 (933 m water depth) was collected in the area of
the western Cretan counter-clockwise gyre (Pinardi and Masetti,
2000) where annual primary productivity (PP) is 125 gC m− 2 yr− 1
(Bosc et al., 2004). The sapropel interval exhibits sharp lower and
upper boundaries; 2 cm of grey sediment occurs up to the sapropel
(transitional layer), passing to oxidised sediment in the upper part of
the studied section. Core BAN89-GC09 was collected south of Crete,
under the path of the surface eastward current lapping North Africa,
where modern annual PP is estimated at ~ 105 gC m− 2 yr− 1 (Bosc et al.,
2004). In this core the 20-cm thick sapropel exhibits sharp lower and
upper boundaries. The sapropel is laminated from 241 cm to
234.25 cm. The next 4 cm are characterised by a significant colour
change (light grey mud–transitional layer), returning to pale yellow
mud at the top of the section. Core BD02-GC01, collected beneath the
Western Ionian Gyre, where annual PP is about 125 gC m− 2 yr− 1 (Bosc
et al., 2004), includes sapropel S5, which is 9-cm thick and
characterised by sharp lower and upper boundaries. Grey sediment
occurs at the top of the sapropel layer (329–327 cm–transitional layer)
in this core, the last 15 cm of which are characterised by light reddish
brown mud. The transitional layer present in the three cores could
correspond to the oxidised part of the sapropel layer, as already
suggested for core BAN89-GC09 by Sangiorgi et al. (2006).
Benthic foraminifera assemblages were investigated in detail and
qualitative and quantitative analyses were performed on the N63 µm
size fraction. Samples containing abundant microfauna have been split
in aliquots, all specimens were counted and the relative abundance of
each species and species richness (S) are reported, all counts being
corrected for splits. Foraminiferal numbers are referred to 1 g of bulk
dry sediment (BFN). For the layers where the age-model is well
constrained (see paragraph on stratigraphic framework) the Benthic
Foraminiferal Accumulation Rate (BFAR) is calculated, based on a
sediment density of 1.43 g/cm3 for the sapropel layer and 1.58 g/cm3
for the homogeneous sediment characteristic of oxygenated bottom
waters (Capozzi, personal communication). Ostracods were also
counted, but not differentiated into species: their abundance is
expressed as number of specimens per dry gram sediment (ON).
Diversity indexes were calculated using PAST software (v. 1.33b)

Table 1
Locality and depth of the cores analysed and used for comparison in the present study

Cores Latitude Longitude Water depth (m) Region Reference

SIN97-GC01 35°49.01'N 22°42.04'E 933 Urania basin area This study
BAN89-GC09 33°37.98'N 24°43.29'E 2011 Napoli Dome This study
BD02-GC01 37°33.90'N 17°48.32'E 2470 Ionian basin This study
KS205 38°11.86'N 18°08.04'E 2384 Ionian basin Cane et al. (2002)
BAN81-23 35°52.03'N 20°27.46'E 3026 Ares Crater area Oggioni and Zandini (1987)
30/2 35°50.05'N 20°50.7'E 2885 Poseidon Plateau Vismara-Schilling and Coulbourn (1991)
ODP971A 33°43'N 24°41'E 2026 South Crete Rohling et al. (2006)
LC21 35°66'N 26°58'E 1522 North-eastern Crete Casford et al. (2003)
M40-4/67SL 34°48.8'N 27°17.8'E 2158 North-western Levantine basin Schmiedl et al. (2003)
ODP967C 34°04.27'N 32°43.53' 2554 Eratosthenes seamount Cane et al. (2002)
KL83 32°36.9'N 34°08.9'E 1433 South-eastern Levantine basin Schmiedl et al. (2003)
 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271 261

(Cane et al., 2002) the results derived from the three cores presented
in this study have been compared with the 971A-equivalent depth
scale (Capotondi et al., 2006). The relative positions between the
correlation markers proposed by Cane et al. (2002), and the change in
colour from light brown to black at the base of sapropel layers in the
three studied cores, appear to be synchronous. Our chronology for S5
relies on a simple linear interpolation between the age of the onset
and the top of the dark layer, suggesting that within the sapropel S5,
1 cm corresponds to ~ 715 year in SIN97-GC01, ~ 260 year in core
BAN89-GC09 and ~ 555 year in core BD02-GC01. The sedimentation
rate for the post-sapropel interval is based on a linear interpolation
between the top of sapropel S5 and the base of sapropel S4 with an
assigned age of 107 Ka (Bar-Matthews et al., 2000) (see Table 2). It is
impossible to calculate the sedimentation rate before sapropel S5,
because there are not clear events in the three cores: sapropel S6 is not
present and also the isotopic signal necessary to determine the
transition from MIS 6 to MIS 5e is incomplete.

3. Results

Fig. 3 summarises the lithological expression of the sapropel S5 in

the three cores, the number of benthic foraminifera (BFN) and
ostracods (ON) per dry gram of sediment along with the Shannon
index [H'(S)] and Evenness index [E] for the benthic foraminiferal
assemblages. BFAR for each core is also presented. The main species
that characterised the pre-sapropel, sapropel and the post-sapropel
layer are illustrated for each core in Figs. 4 to 6. In each case, single
species are illustrated when these are particularly abundant or when
their ecological significance is useful to determine the evolution of the
sea floor. In other cases, species or genera are grouped based on life
Fig. 2. Schematic lithological log and stratigraphical position of the sapropel S5.
Calcareous nannofossil biostratigraphy is based on Giunta et al. (2006).
strategies, as explained in the Section 1.1.

3.1. Core SIN97-GC01 — Fig. 4 and Table 3

(Hammer and Harper, 2005). The following diversity measures were
The BFN exceeds 2000 specimens in the pre-sapropel interval with
calculated: Shannon–Wiener index (ln) [H(S)], and the Evenness index
exception of some levels, at the bottom of the core and at 296 cm
[E]. Shannon index and Evenness are commonly used measures of
(BFN b 1600). BFN strongly decreases in the sapropel and post-
diversity in ecological and foraminiferal studies. Evenness index [E] is a
sapropel layer (average values of 365 ind. g− 1, SD (standard
measure that quantifies how equally specimens are distributed
deviation) = 131 and 311 ind. g− 1 (SD = 165) respectively), with a
amongst species. Values of the evenness index [E] are constrained
small peak in the transitional layer (793 ind. g− 1). BFAR shows the
between 0 and 1. The less the variation in the abundance of species, the
same trend of the BFN but with an evident increase in the transitional
higher the Evenness index [E]. Benthic Foraminiferal Oxygen Index
layer. More than 128 taxa have been identified, the most common
(BFOI) was calculated following Kaiho (1999) together with the oxygen
species being Globocassidulina subglobosa, Cassidulina crassa, Bolivina
index proposed by Schmiedl et al. (2003).
catanensis, Eponides pusillus and Fissurina spp. In the pre-sapropel
layer, Cassidulina carinata and miliolids dominate the assemblage,
2.1. Stratigraphic framework
Bolivina spp. and phytodetritus taxa are also present. A peak of deep-
infaunal taxa together with decreasing numbers of miliolids char-
Sapropel S5 was deposited during the warm and humid period of
acterise the first centimetres of the sapropel layer, whereas the upper
Marine Isotope SubStage (MIS) 5e, representing fully developed
interglacial conditions characterised by ~ 5 °C rise in Atlantic Ocean
sea surface temperature (Shackleton et al., 2003) and sea level ~6 m
above present (Bard et al., 1996). Slightly different time intervals for Table 2
the deposition of sapropel S5 have been suggested. Bar-Matthews Age versus depth of stratigraphic fixed points. The top and the base of the sapropel S5
et al. (2000), Rohling et al. (2002) and Cane et al. (2002) proposed the indicate the lower and upper lithological limit of the dark layer
interval 124–119 ka BP, Struck et al. (2001) suggested 128–123 ka BP, Event Age Core
and Emeis et al. (2003) 127–122 ka BP. Notwithstanding these (ka BP) SIN97-GC01 BAN89-GC09 BD02-GC01
differences, all authors propose that the deposition of sapropel S5 Base S4 (cm) 107 206 169 304
lasted 5000 years. The base of the sapropel is adjusted to the age given Top transitional phase (cm) 283 230 327
in Table 2, which coincides with maxima in Northern Hemisphere Top S5 (cm) 119 285 234.25 329
summer insolation (Rossignol-Strick and Paterne, 1999). Sapropel Base S5 (cm) 124 292 254 338
Width of the dark layer (cm) 7 19.75 9
deposition is believed to be initiated by a significant hydrographical
S5 Sedimentation rate (cm/ka) 1.4 3.95 1.8
event related to an increasing intensity of moisture due to the Top S5 — Base S4 interval 79 65.25 25
intensification of the summer monsoon, suggesting a very rapid width (cm)
response of the Eastern Mediterranean Sea to enhanced precipitation Top S5 — Base S4 interval 6.58 5.43 2.08
in the surrounding catchments (Emeis et al., 2003). Using the sedimentation rate (cm/ka)
1 cm = years 152 184 480
statistical multiproxy correlation approach for records spanning S5
 262
C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271
Fig. 3. Photograph of the half cores SIN97-GC01, BAN89-GC09 and BD02-GC01. Note the dark sapropel layer (S5) indicated by the shaded area. The dashed line indicates the upper boundary of the transitional phase. Number of benthic
foraminifera per dry gram sediment (BFN), number of ostracods per dry gram sediment (ON), Benthic Foraminiferal Accumulation Rate (BFAR), Diversity [H'(S)] and Evenness [E] of benthic foraminifera assemblage are shown for each core. The
age intervals provided (at right) are based on linear interpolation between estimated ages of 124 and 119 ka BP for the onset and the end of sapropel S5 based on Rohling et al. (2002).
 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271 263

Fig. 4. Abundance of selected benthic foraminiferal species in core SIN97-GC01. Phytodetritus and deep-infaunal groups are faunal cluster explained in Section 1.1. Shaded interval
represents the sapropel layer and the dashed line indicates the upper boundary of the transitional phase. The age interval provided (at right) is based on a linear interpolation
between estimated ages of 124 and 119 ka BP for the onset and the end of sapropel S5, based on Rohling et al. (2002).

levels are characterised by increased percentages of Cassidulina crassa,
Fissurina spp., Globocassidulina subglobosa, phytodetritus taxa, and the
disappearance of infaunal taxa. A peak of Articulina tubulosa is
observed in the upper level of the sapropel layer. The transitional
layer is characterised by a high percentage of Bolivina spp., the
occurrence of deep-infaunal taxa and a peak of Gyroidinoides
laevigatus, together with the phytodetritus taxa. The benthic for-
aminiferal diversity [H'(S)] varies from 1.8 to 3.1 and exhibits short-
term fluctuations throughout the whole core. Diversity slightly
decreases (average of 2.5) during the formation of sapropel S5. At
284 cm, a small increase of diversity [H'(S) = 3] indicates the end of the
sapropel deposition. In the post-sapropel layer, the average value of
the Shannon index is 2.8. Evenness has an opposite trend compared to
the Shannon index with short-term fluctuation along the whole core
but with higher values in the sapropel layer (0.76) than in the pre and
post-sapropel levels (0.71) (Table 3).
In the pre-sapropel layer, the ostracod number (ON) is 243 ind. g− 1
on average, whereas within the sapropel layer ostracods are very rare
264 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271

Fig. 5. Abundance of selected benthic foraminiferal species in core BAN89-GC09. Phytodetritus and deep-infaunal groups are faunal cluster explained in the Section 1.1. Shaded
interval represents the sapropel layer and the dashed line indicates the upper boundary of the transitional phase. The age interval provided (at right) is based on linear interpolation
between estimated ages of 124 and 119 ka BP for the onset and the end of sapropel S5, based on Rohling et al. (2002).

or absent. In the post-sapropel, ON displays a small increase, reaching
an average value of 27 ind. g− 1.
3.2. Core BAN89-GC09 — Fig. 5 and Table 4
BFN varies from an average value of 166 ind. g− 1 (SD = 76) in the
pre-sapropel interval to 12 ind. g− 1 (SD = 7) during the sapropel
deposition. In the post-sapropel interval, BFN increases to an average
value of 33 ind. g− 1 (SD = 17), with a peak of 67 ind. g− 1 in the
transitional layer. BFAR values are low during sapropel deposition,
reaching zero in several samples, but exhibit an important peak in the
transitional layer. After the transitional layer BFAR again decreases.
The dominant species in the pre-sapropel layer are Anomalinoides
minimus and Eponides pusillus, with small percentages of Gyroidi-
noides laevigatus, Fissurina spp., and Cassidulina carinata. In the
sapropel layer Bolivina spp. are present, together with G. subglobosa,
although always in very low abundance. At the top of the sapropel
different taxa successively dominate the benthic assemblage. Fissurina
spp. first increases together with G. laevigatus, followed by Articulina
tubulosa and finally Anomalinoides minimus. Diversity [H'(S)] in the
 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271 265

Fig. 6. Abundance of selected benthic foraminiferal species in core BD02-GC01. Phytodetritus and deep infaunal cluster explained in the paragraph 1.1.Section 1.1. Shaded interval
represents the sapropel layer and the dashed line indicates the upper boundary of the transitional phase. The age interval provided (at right) is based on linear interpolation between
estimated ages of 124 and 119 ka BP for the onset and the end of sapropel S5, based on Rohling et al. (2002).

pre-sapropel layer is on average about 2.6 and strongly decreases in
the sapropel with values b1. The benthic fauna is absent in only one
sample (244 cm), although the sapropel layer yields only 2–4 species.
In the pre-sapropel layer, Evenness is rather low with values around
0.4, but shows a rapid increase in the sapropel layer. Mean post-
sapropel evenness is higher than in the pre-sapropel layer with [E]
value around 0.8.
The number of ostracods per dry gram sediment in the pre-
sapropel layer has the same trend as the density of foraminifera, even
if the total number is very low (average 300 ind. g− 1). They disappear
during sapropel deposition but occur again after the end of the dark
layer deposition (Table 4).
3.3. Core BD02-GC01 — Fig. 6 and Table 5
The BFN varies from an average value of 46 ind. g− 1 (SD = 17) to
2 ind. g− 1 (SD = 2 excluding the maximum value of 22 ind. g− 1) from
the pre-sapropel to the sapropel layer. In the interval between 335 and
266 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271
330 cm, benthic foraminifera are absent, with exception of cm 331
where 5 ind. g− 1 are present. At 329 cm, benthic foraminifera reappear
with an average value of 27 ind. g− 1 (SD = 32) in the post-sapropel
layer. BFAR shows the same trend of BFN. A similar suite of species
characterise the pre-sapropel and post-sapropel layers, but they show
different abundances: Anomalinoides minimus, Gyroidinoides laeviga-
tus, Quinqueloculina seminulum, and Eponides pusillus are more
abundant in the pre-sapropel than in the post-sapropel layer. On the
other hand, Globocassidulina subglobosa, Articulina tubulosa and Boli-
vina catanensis are present only in the post sapropel interval. In the
transitional layer different taxa successively dominate: Fissurina spp.
first reappears afterward Articulina tubulosa increases together with
Anomalinoides minimus. In pre-sapropel layer benthic foraminiferal
diversity [H'(S)] ranges between 1.9 and 1.1 and is generally lower than
in core BAN89-GC09. Within the sapropel, diversity drops significantly
to a minimum average value of 0.7 in levels that are not barren of
microfauna and evenness shows an opposite trend (Table 5).
Ostracods are very rare, with a maximum density of 10 ind. g− 1 in
the pre-sapropel levels; at 338 cm they disappear and occur again at
322 cm.
4. Discussion
4.1. Comparison with previous studies
Many studies dealing with benthic foraminifera and sapropels
have focussed on sieve fractions N125 µm or coarser (among others
Rohling et al., 1997; Kuhnt et al., 2007; Abu-Zied et al., 2008). In
particular, previous studies on foraminiferal assemblages of sapropel
S5 (see Jorissen, 1999 for a review), were performed on size fractions
N150 µm. A recent paper (Schmiedl et al., 2003) described results
based on size fractions N125 µm; the finer size fraction 63–125 µm
was analysed for only a few selected levels. In the present study, the
lower limit of 63 µm is adopted because some small species, such as
Epistominella exigua, Eponides pusillus, other small rotaliids and
bolivinids, could be underestimated if a coarser size fraction is chosen.
In fact, foraminifera vary enormously in size from minute agglutinated
spheres (10–30 µm) to giant xenophyophores 10 cm or more (Gooday
et al., 1995). The dimensions of the calcareous benthic foraminifera,
which are the main constituent of fossil assemblages, vary also from
tiny (rotaliids and bolivinids) to meiofaunal dimensions (miliolids and
lagenids; Sabbatini et al., 2004). In an environment characterised by
extreme conditions, such as seafloor dysoxia, low salinity or carbonate
corrosive waters, small species can represent an important part of the
benthic foraminiferal community (Boltovskoy et al., 1991; Shepherd
et al., 2007). In particular, as suggested by Schröder et al. (1987), the
lower size limit of 63 µm provides a more reliable statistical basis for
paleoceanographic studies. The use of coarser size fractions involves a
significant loss of specimens and tends to create artificial “barren”
zones in sequence dominated by small-sized species (Schröder et al.,
1987). Shepherd et al. (2007) suggest that smaller species, concen-
trated in finer (63–150 µm) size fractions are important for
assessments of foraminiferal assemblages in dysoxic, organic-rich
environments.
Oggioni and Zandini (1987) analysed the N63-µm size fraction of
sapropel S5 in a core (BAN81-23) collected in the Ares Crater at 3026-m
water depth (Fig. 1). They sampled at intervals of 10 cm across sapropel
S5, which has a thickness of 36 cm. In the three samples collected in the
sapropel layer, BFN was higher than zero (3 to 8 ind. g− 1) and
resedimentation was observed only in the middle sample (21 ind. g− 1).
The dominant species in this interval were Anomalinoides minimus,
Bolivina pseudoplicata, Eponides tumidulus (= Eponides pusillus), Cassi-
dulina subglobosa and Cassidulina crassa. Another paper published by
Vismara-Schilling and Coulbourn (1991) analysed sapropel S5 in core
30/2 collected on the Mediterranean Ridge, Poseidon Plateau, at 2885-
m water depth. Three samples were collected and analysed in this core,
in which the sapropel is 15 cm thick. BFN values were always very low
(0.8 to 2.4 ind. g− 1) and benthic foraminifera were absent in one
sample. Species of Bolivina, dominated by B. pseudoplicata, were most
abundant, together with rotaliids. In both cases, the low resolution of
the sampling means that trends in the density and occurrence of
benthic foraminiferal species are not clearly apparent, and a detailed
reconstruction of changes in the sea-floor environment during the
transition oxic–dysoxic/anoxic condition is not possible. Nevertheless,
these papers are important because they document the presence of
benthic foraminifera in the sapropel layer. Moreover, the species found
in these previous studies are the same as those identified in the three
cores analysed during the present investigation.
Other studies (Parisi, 1983; Nolet and Corliss, 1990; Rohling et al.,
1993; Kuhnt et al., 2007; Abu-Zied et al., 2008) based on coarser size
fraction, reported sapropel levels in which benthic foraminifera were
absent. These barren levels could be due to the hostile environment or
they could be artefacts created by the use of a coarser sieve. In core
KL83 (1433-m water depth), Schmiedl et al. (2003) reported benthic
foraminifera in the first part and the upper half of the S5 sapropel
(fraction N125 µm). In the shallowest core of the present study (SIN97-
GC01), the BFN (as well as BFAR) strongly decreases in the sapropel but
the sediments are never devoid of foraminifera; the sapropel-fauna
contains a few specimens of G. subglobosa, C. crassa, Bolivina spp., and
Fissurina spp. together with subordinated E. pusillus and other small
rotaliids. All the species present in the sapropel layer have an average
size less than 150 µm. In the deepest cores, benthic foraminifera are
always very rare and small in size; in core BD02-GC01 the entire S5
interval is barren of benthic foraminifera. However, it can not be
excluded that foraminifera occurring in the sapropel layers have been
transported down-slope. Even if it is quite easy to recognise taxa
transported from shallower water, resedimentation events that
involve a more limited depth-range are not easy to recognise. As
suggested by Jorissen (1999), increased faunal densities associated
with sapropels, which are accompanied by an increase in the number
of species, should be considered with care as they can result from
down-slope transport. In the case of the three cores examined in the
present study, the density and diversity show an abrupt decrease and
the specimens found in these layers are well preserved and do not
show evidence of transport. Furthermore, the species present in these
particular levels are small rotaliids and Bolivina spp. that normally live
in the deepest part of the basin and are tolerant of low-oxygen
concentrations. The composition of the benthic microfauna, the trend
of BFN and of BFAR, and the lack of obvious resedimentation layers,
corroborate the hypothesis that the benthic foraminiferal microfauna
is autochthonous.
4.2. Benthic ecosystem variability in the Eastern Mediterranean Sea
pre- during and post-sapropel S5 deposition
Several studies have investigated the combined influence of water
depth and food availability on benthic microfaunal composition
(Jorissen, 1987; Carney, 1989; De Stigter et al., 1998). De Rijk et al.
(1999, 2000) illustrate the relationship between deep-sea foraminif-
eral microfauna and the decreasing food availability with increasing
water depth in the Mediterranean Sea. Ecological studies (Gooday,
1993, 2003; Gooday et al., 1998) demonstrate that the diversity of
benthic marine assemblages is also strongly dependant on the stability
of the environment and the timing of the organic input. A stable
ecosystem allows a well-diversified community, whereas ecosystems
subject to strong fluctuations sustain a less diversified benthic fauna
dominated by opportunistic taxa. The equation of Berger and Wefer
(1990) predicts that the amount of organic matter reaching the
seafloor is proportional to the primary productivity but also depends
on the square of the depth. This means that the deeper the basin the
less organic matter reaches the seafloor. According to the relation
proposed by Herguera and Berger (1991) for 1 g of organic matter that
 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271
reaches the seafloor one benthic foraminiferal shell (N150 µm) is
generated. Thus the BFAR can be used as a proxy for organic flux to the
seafloor, as long as the sedimentation rate is constant.
Several studies indicate that oligotrophic environments support
fewer benthic foraminifera, but when the organic flux to the sea floor
increases, BFAR values also increase strongly (Loubere, 1994). Of
course, this equation cannot strictly apply to the present study
because 1) the size fraction analysed was N63 µm rather than
N150 µm; 2) it is not possible to calculate BFAR in the pre-sapropel
interval and 3) low oxygen concentrations have a major impact on the
benthic microfauna (Naidu and Malmgren, 1995). Changes in the flux
of organic carbon to the sea-bed causes shifts in the faunal
composition. Such shifts have been recognised in the studied cores.
The benthic assemblage composition and faunal trends through the
studied interval were similar in cores BAN89-GC09 and BD02-GC01.
Core SIN97-GC01, on the other hand, yielded different species
assemblages and the trends in BFN and BFAR were slightly different
from those observed in the other cores. Different water depths
together with different PP and hence different organic flux rates to the
seafloor (Jz) may be the main causes of this difference between the
sites. In fact, during the oxygenated interval (pre-sapropel), the BFN in
core SIN97-GC01 was more than 10 times higher than in core BAN89-
GC09 and 50 times higher than in core BD02-GC01. The position of
core SIN97-GC01 is optimal for the development of the benthic
microfauna due to the shallow location (recent Jz = 234 gC/m2/year
calculated with formula of Berger and Wefer, 1990) and proximity to
the continental shelf, which supplies additional organic matter. At this
site, a rich and diverse benthic foraminiferal assemblage develops. It
consists mainly of bolivinids, Cassidulina carinata, Fissurina spp.,
miliolids, phytodetritus taxa, and even includes subordinate numbers
of deep-infaunal taxa. According to the TROX model of Jorissen et al.
(1995), the combination of a moderate flux of organic matter and
elevated concentrations of oxygen above and in the sediment results
in the occupation of both epifaunal and deep infaunal niches. In the
deepest cores (BAN89-GC09 and BD02-GC01), foraminiferal densities
in the pre-sapropel sediments are lower with a high percentage of G.
laevigatus and phytodetritus taxa that indicate an oligotrophic, well-
oxygenated environment. The positive correlation between benthic
foraminiferal density and organic flux to the seafloor applies until the
oxygen level drops below a critical value (Naidu and Malmgren, 1995;
Morigi et al., 2001). Only specialised taxa can survive in dysoxic
conditions, and hence, if dysoxia or anoxia persist, BFAR dramatically
decreases and benthic foraminifera eventually disappear. A drop in the
abundance of miliolids before the onset of sapropel deposition,
combined with a decreases in BFAR and BFN and an increase of low-
oxygen indicators (infaunal taxa), suggest a strong decrease in oxygen
concentrations. The peak of species, such as Globobulimina spp. and
Chilostomella spp., which consume degraded rather than fresh organic
material, suggests increasing preservation of the organic matter at the
seafloor, favouring the development of faunas feeding on low-quality
food sources. In both the deepest cores, there is a strong increase in
the abundance of phytodetritus taxa after the peak of deep-infaunal
taxa and before the disappearance of the benthic microfauna. The
presence of phytodetritus taxa suggests that pulsed inputs of labile
organic matter triggered seafloor oxygen depletion.
A previous study (Weldeab et al., 2003) estimated a Jz value of
350 gC m− 2 yr− 1 during the deposition of sapropel S5 in the area of
core BAN89-GC09, about three times higher than present values
(PP = 106 gC m− 2 yr− 1, Jz = 123 gC m− 2 yr− 1). This corresponds to a very
high export production, similar to that reported in modern upwelling
areas (Berger, 1989). At the shallower site (SIN97-GC01), the presence
of phytodetritus species again points to pulsed organic-matter inputs,
while the low abundance of taxa feeding on degraded material
indicates higher oxygen concentrations. The disappearance of ostra-
cods with decreasing seafloor oxygen concentrations suggests that
these metazoans are more sensitive to oxygen depletion than benthic
267
foraminifera. Although BFAR values are quite different, similar down-
core trends in the three cores imply a similar evolution of the benthic
environment: elevated values of BFN in the pre-sapropel levels
indicate optimal conditions for benthic life, followed by a strong
decrease (not reaching zero) when organic carbon started to
accumulate (corresponding to the onset of the dark level), and low
abundance and/or barren levels in the sapropel sensu strictu. Above
the sapropel, where the sediment colour changes from black to grey, a
peak of BFAR marks a transitional phase in the three cores. This peak is
characterised by the re-occurrence of Fissurina spp., followed by Ar-
ticulina tubulosa and phytodetritus taxa. This foraminiferal succession
that occurs at the deepest sites at the end of the sapropel deposition
indicates that the re-oxygenation was fast enough to allow the
phytodetritus taxa to colonise the sea bottom (Jorissen, 1999). After
the transitional phase, benthic foraminiferal density remains low, and
miliolids increase, indicating a return to oligotrophic and well-
oxygenated environment. The low BFAR recorded at the three sites
indicates a slow ecosystem recovery. About 5 kyr after the termination
of sapropel deposition, the benthic environment totally recovered, as
testified by the high value of BFAR at the top of the studied interval in
core BD02-GC01. Ostracods, however, recover more slowly at the end
of the sapropel deposition and return only after the transitional phase.
The similar trends of BFN and BFAR recorded in the three sites suggest
that the seafloor environment in the Eastern Mediterranean was
characterised by low oxygen concentration during sapropel deposi-
tion, although with different intensities in the different areas, as
discussed in the next section.
4.3. Evolution of the anoxia at the sea bottom and short term variability
The isotopic signal of shallow-dwelling Globigerinoides ruber and
the absence of deep-dwelling planktonic foraminifera such as Glo-
borotalia inflata, indicate that the onset of sapropel S5 deposition
coincided with a rapid increase in surface-water stratification that
inhibited the deep-water formation and resulted in anoxic condition
in the deep Mediterranean basins (Rohling et al., 2006). Although,
benthic foraminifera, as a group, are extremely tolerant of severe
oxygen depletion and can survive long periods of dysoxia/anoxia
(Josefson and Widbom, 1988; Bernhard and Reimers, 1992; Risgaard-
Petersen et al., 2006), they were strongly impacted by this long-term
oxygenation crisis. Across the investigated intervals, BFAR (and BFN)
values exhibit strong fluctuations that can be attributed to extensive
and drastic decreases in oxygen concentrations at the seafloor (Fig. 2).
In particular, in the deepest core (BD02-GC01), the absence of benthic
microfossils indicates persistent anoxia during the time of the
sapropel deposition. On the other hand, some intervals in core
BAN89-GC09 show a very low BFAR (and BFN) value and in the
shallowest core SIN97-GC01 the sediment is never barren of benthic
foraminifera. To illustrate the changes in oxygen concentrations
during the deposition of the sapropel S5, the Benthic Foraminiferal
Oxygen Index (BFOI) of Kaiho (1999), and the oxygen index proposed
by Schmiedl et al. (2003), were calculated for the three cores (Fig. 7).
These paleo-oxygenation proxies are discussed in detail by Jorissen
et al. (2007), who highlight some pitfalls for both indexes. One of the
main problems is that all the species respond to organic flux increases
as well as decreases in bottom-water oxygenation. Furthermore
Kahio's index is based on oxic, suboxic and dysoxic indicators that
are not calibrated with respect to recent faunas. It is therefore
important to remember that, in the three cores analysed during the
present study, variations in these two oxygen indexes are always
accompanied by a strong decrease in the number of foraminiferal tests
per gram dry sediment, and that the sapropel levels contain a low-
diversity fauna, strongly dominated by opportunistic taxa (phytode-
tritus taxa or deep infauna).
The two indexes suggest that suboxic condition (oxygen content
between 0.3and 1.5 ml/l) developed abruptly. The sudden
268 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271

Fig. 7. Records through sapropel S5 of the benthic foraminiferal oxygen index (BFOI) (Kahio, 1999) and the index proposed by Schmiedl et al. (2003). The grey scale shows the
empirical relation between BFOI and dissolved oxygen levels, as calculated by Kaiho (1999). The stable oxygen isotope record for the planktonic foraminifera Globigerinoides ruber is
provided by Capotondi et al. (2006). Grey blocks indicate the visual extent of the dark coloured sapropel sediments in each core, dashed line indicates the upper boundary of the
transitional phase and the solid lines represent primary correlation levels between the studied sites (Capotondi et al., 2006) and the stratigraphic framework proposed by Cane et al.
(2002). The stratigraphic marker i6 corresponds to the prominent shoulder before sharp enrichment trend of δ18O G. ruber and stratigraphic marker f4 corresponds to the
disappearance of Globorotalia scitula in the planktonic assemblage.

disappearance of oxic species, combined with the strong decrease of
BFAR (BFN) values, reflects the development of the dysoxic/anoxic
conditions in the Mediterranean Sea. Comparison between the
records from the deepest cores suggests that anoxia developed first
in the southern Mediterranean area (core BAN89-GC09) and then in
the Ionian Sea (core BD02-GC01). Considering the sedimentation rate
calculated for the two cores (see Table 2), there is a gap of about 500 yr
between the development of anoxia at the site of BAN89-GC09 and at
the site of core BD02-GC01. This delay in the onset of persistent anoxia
between the two cores could be due to several factors. First, there is a
difference in water depth between the cores. One hypothesis is that
the delayed onset of anoxia at BD02-GC01 (the deepest site) could
reflect a slow downward expansion of the oxygen minimum zone, as
proposed by the model of Strohle and Krom (1997) and Stratford et al.
(2000). A second hypothesis is that anoxia developed later in the
northernmost sector. Cane et al. (2002) observed a delay in sapropel
deposition in the easternmost sector (ODP976C — Eratosthenes
seamount) and suggested that this time difference could be due to
lower productivity/export production, or to a period of occasional
deep water ventilation. The site of core BD02-GC01 is affected at
present by injection of oxygenated deep-water formed in the Adriatic
Sea. This process could have influenced this site also during the time of
sapropel S5 deposition and delayed the onset of anoxia. When
bottom-water ventilation collapsed in the Ionian Sea, anoxia persisted
until 124 ka BP, whereas in the south Mediterranean Sea (core BAN89-
GC09) the situation may have been more variable. The two oxygen
indexes in core BAN89-GC09 yield inconsistent results in the sapropel
layer: Schmiedl's index does not show strong fluctuations during
sapropel deposition whereas BFOI shows a more variable trend. In fact,
in several levels the presence of oxic/dysoxic indicators together with
a small peak of BFAR, corresponding to an increase of BFOI, suggests
that the input of oxygenated water at the seafloor led to the re-
establishment of a benthic population. In core BAN89-GC09, which
has the highest sedimentation rate (3.95 cm/ka), a repopulation event
involving the reappearance of oxic indicators suggests that there was a
marked variability in oxygen concentrations. This event, which is
confirmed by a BFOI peak in the interval 249–246 cm (oxygen content
N3.2 ml/l, on the base of Kahio index), could indicate instability of the
water column or an abrupt injection of deep oxygenated water.
Considering a depositional period of 5 ka for the duration of S5, this
short event lasted about 800 years. Although it left no lithological
trace in the sapropel layer, other proxies can be used to identify this
short episode. In particular, it corresponds to a peak in the abundance
of the deep dwelling planktonic foraminifera Globorotalia scitula
(Capotondi et al., 2006). In the stratigraphic framework proposed by
Cane et al. (2002), the disappearance of this species is indicated as
correlation point f4 (Fig. 7). Rohling et al. (2002) reported that the
peak coincides with a δ 18OG.ruber anomaly in the Ionian Sea and in the
south Mediterranean Sea. According to these authors, this depletion in
the δ18OG.ruber indicates a relaxation of the northward penetration of
the Intertropical Convergence Zone (ITCZ) that limits the duration of
the monsoon to 1–2 month in the area of the Libyan basin. The oxygen
 C. Morigi / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 258–271
isotope depletion is also recorded in our cores. Following Cane et al.
(2002) the correlation point i6 indicates the prominent shoulder
before the sharp enrichment trend of δ18OG.ruber(Fig. 7). In our record,
this oxygen isotope depletion corresponds to the increase in BFOI,
although this event is not reflected by the Schmiedl Index. Sangiorgi
et al. (2006) found evidence for it in the same core using a multiproxy
approach and suggest that it reflects upper water column mixing
together with a decrease in temperature and an increase in seasonal
contrast. This event is not evident in core BD02-GC01. At this site,
anoxic conditions that persisted until the end of sapropel deposition
and/or the low sedimentation rate (1.8 cm/ka) could mask the record
of this brief event.
A different situation is represented in core SIN97-GC01, where a
low BFAR in the sapropel layer is represented by a mixture of oxic and
dysoxic species. Both the BFOI and the Schmiedl index indicate that
the bottom water never became anoxic and the presence of benthic
fauna demonstrates that oxygen was consistently available at 933 m
depth, although at low concentration. The occurrence of benthic
foraminifera in the late phase of sapropel S5 formation was already
described by Schmiedl et al. (2003) in a core collected near the Israeli
margin at a water depth of 1433 m. These authors suggest that a
gradual cooling may have favoured the formation of dense water at
intermediate and deep formation sites. The continuous presence of
benthic foraminifera in core SIN97-GC01 through sapropel S5 implies
that persistent anoxia did not develop in that region. In the modern
Black Sea, which is anoxic below 150 m depth, several authors
(Codispoti et al., 1991; Özsoy and Ünlüata, 1997) have described the
structure of the chemocline as a dome, i.e. shallower in the middle of
the basin and deeper near the shelf. Rohling et al. (2006) estimate the
depth range of the chemocline in the middle of the Eastern
Mediterranean Sea to have been 150–300 m during S5 deposition
and suggest that the cyclonic circulation may have caused the
chemocline to reside considerably deeper near the margins of the
basin. A chemocline at about 1000 m water depth is needed to explain
the presence of a stressed benthic microfauna in the shallower core. A
second hypothesis is supported by the model of Maldonado and
Stanley (1976), who suggested that a partly ventilated water mass
existed between 1000 and 2000 m depth and that the deepest part of
the basin was occupied by stagnant and anoxic water. Finally, a third
hypothesis was proposed by Casford et al. (2003), who suggested that
intermittent bottom-water ventilation occurred throughout periods of
sapropel deposition, creating high-frequency variability in deep-water
formation. These authors proposed that a blanket of anoxia developed
under areas of higher productivity, and frequent intermittent bottom-
water ventilation occurred throughout periods of sapropel deposition.
In area of low productivity, there was no bottom-water anoxia, but
poor ventilation created dysoxic conditions, allowing the observed
persistence of specialised benthic foraminifera.
It is impossible to decide which, if any, of these hypotheses is
correct based on benthic foraminiferal data from only three cores.
However, the data reported here suggest that although the overall
ventilation in the Eastern Mediterranean Sea was much reduced,
regional differences existed in the intensity and frequency of the
bottom-water oxygen depletion.
5. Conclusions
The onset of sapropel deposition is normally considered to be
coincident with the disappearance of benthic foraminifera. However
the studied cores reveal a different situation characterised by high
internal and spatial variability in the sapropel. The onset of the
sapropel deposition is characterised by a strong decrease of the
benthic foraminiferal number due to the low-oxygen conditions at the
seafloor. On the Mediterranean margin, poor ventilation created
dysoxic condition allowing the presence of a stressed benthic
microfauna. At the deeper stations ventilation collapsed completely
269
in response to the change in hydrographic forcing and organic flux to
the seafloor. As a result, the seafloor remained anoxic for the entire
duration of the sapropel deposition. However, a short, cold event
recorded in the southern part of the Mediterranean Sea indicate
instability in the water column and a partial re-oxygenation of the
seafloor that allowed brief colonisation of benthic foraminiferal
microfauna. At the end of the sapropel deposition, during the
transitional phase, the oxygen concentration increased strongly as
indicated by the presence of taxa that require a high oxygen
concentration. The environment did not return to its pre-sapropel
condition, or improve enough to allow a total re-colonisation of the
seafloor.
Analyses of the 63 µm fractions yielded more information on the
benthic assemblage during stress episodes than coarser fractions,
making it possible to evaluate benthic ecosystem variability. In fact,
small taxa dominated foraminiferal assemblages when the environ-
mental conditions at the seafloor were unfavourable to the benthic
life. In particular, Fissurina, a genus that normally is not considered in
this type of study due to its small size and poorly-known ecological
requirements, seems to play an important role in the re-colonisation
of the seafloor at the end of the sapropel deposition and is the first
taxon to reappear during the transitional phase after the sapropel
deposition.
Acknowledgements
Special thanks go to S. Giunta, A. Negri and A. Sabbatini for their
constructive comments and discussions. I would like to thank warmly,
A. Gooday which significantly helped to improve the manuscript. E.
Thomas and an anonymous reviewer are kindly acknowledged for
their helpful and critical review of the manuscript. This research is
part of the project “The dynamic of the Mediterranean paleoecosys-
tem during the Eemian” (Coord. C. Corselli) funded by the Italian
MIUR.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.palaeo.2008.10.010.
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285

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Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Organic geochemistry and paleoenvironment of the Early Eocene “Pesciara di Bolca”

Konservat-Lagerstätte, Italy
Lorenz Schwark a,⁎, Annalisa Ferretti b, Cesare Andrea Papazzoni b, Enrico Trevisani c
a
University of Cologne, Institute for Geology and Mineralogy, Zuelpicher Str. 49a, D-50674 Cologne, Germany
b
Dipartimento di Scienze della Terra, Università di Modena e Reggio Emilia, L.go S. Eufemia 19, I-41100 Modena, Italy
c
Museo di Storia Naturale di Ferrara, Via De Pisis 24, I-44100 Ferrara, Italy

A R T I C L E I N F O A B S T R A C T

Article history: Exceptional preservation of fossils in so-called Konservat-Lagerstätten requires specific depositional regimes
Received 20 December 2007 excluding disturbance of bottom sediments by either wave actions and currents or by benthic fauna. We here
Received in revised form 13 March 2008 describe a depositional model for the Eocene “Pesciara di Bolca” Konservat-Lagerstätte based on sedimentological,
Accepted 14 March 2008
paleoecological, and detailed organic geochemical results. Sediments were deposited in a lagoonal-like basin with
stagnant bottom waters located on an extended carbonate platform that was sheltered from open marine waters
Keywords:
Biomarkers
by a submarine threshold. Run-off from nearby land areas provided nutrients to support an algal community
Highly branched isoprenoid dominated by diatoms. No fossil diatom shells have been identified, but evidence for their presence is given by the
Diatoms high abundance of highly branched isoprenoids in extractable bitumens. Influx of terrigenous organic matter into
Anoxia the lagoon occurred in particular during deposition of the basal fish-bearing level L1. Here not only plant
Fossilization macrofossils, amber, spores and pollen but also the lipid composition indicated notable input of land plants via the
Plattenkalk presence of n-C24 to n-C32 carboxylic acids, long-chain n-alkanes (n-C27, n-C29, n-C31) and angiosperm wax
Lithographic limestone triterpenoids. The redox regime in general was strongly reducing as evidenced by the high concentration of sulfur
Solnhofen
vs. organic carbon, excellent kerogen preservation as shown by high hydrogen indices, and low pristane/phytane
but high phytane/n-C18 ratios. The water column was highly stratified with anoxic saline bottom and fresh surface
waters. Euxinic conditions with free reduced sulfur present in the photic zone could only be detected in sediments
from the L1 horizon via traces of aromatic carotenoids derived from green sulfur bacteria (chlorobiaceae), which
utilize H2S in anoxygenic photosynthesis. The depositional regime is thus comparable to the lithographic
limestones of Solnhofen but based on biomarker evidence lacks the high salinities postulated for the latter.
Biomarker composition indicates that best preservation conditions prevailed in the basal part of the studied
section (0–7 m above datum) but declined upon deposition of the upper part. We interpret the body of the
Pesciara as a parasequence of the 4th order (0.01–0.5 Ma), with the lower part representing a relative sea-level
lowstand and the upper part a relative sea-level highstand.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction While the former leads to an entombment of preferentially benthic

Reconstruction of past environments depends on the interpreta-
tion of fossil remains, most of which are shelly and thus induce a
preservation bias in that non-shelly faunas are rarely preserved and
available for investigation. Under special condition, however, even
soft-bodied organism may be preserved in exceptional detail in so-
called Fossil-Lagerstätten. These can be divided into concentration
deposits and conservation deposits after Seilacher (1970) or Allison
(1988). The conservation deposits, synonymous to Konservat-Lager-
stätten, are related to two major processes: obrution or stagnation.
⁎ Corresponding author.
E-mail addresses: lorenz.schwark@uni-koeln.de (L. Schwark), ferretti@unimore.it
(A. Ferretti), papazzoni@unimore.it (C.A. Papazzoni), consgeol@comune.fe.it
(E. Trevisani).
organisms by rapid or catastrophic sedimentation, the latter also
includes water- or even airborne fauna embedded in sediments
accumulating in a low hydrodynamic energy regime with reduced
water mixing, characteristic of stagnant basins (Seilacher, 1970, 1990).
Konservat-Lagerstätten while depending on exceptional circumstances
of accumulation and preservation are not evenly distributed in time
and space (Allison and Briggs, 1993). Peaks in outcrop-normalized
occurrence of Konservat-Lagerstätten are coupled to the prevalence of
particular environments (Allison, 1988) or evolutionary events (Briggs,
2003). In the Cambrian, potentially the lack of invertebrate grazers or
deep bioturbators, in the Carboniferous the widespread high pro-
ductivity regimes in coastal delta plains may have favoured preserva-
tion (Briggs, 2003). The Jurassic yields high numbers of Konservat-
Lagerstätten due to the extended shelf areas on the NW-margin of the
Tethyan Ocean. Here either extensive carbonate platforms with intra-
platform depressions surrounded by microbial or sponge reefs

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.03.009
 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285
restricted circulation and thus favoured deposition of fine-grained
carbonates in Plattenkalk-facies of the Solnhofen type, or transgressive
black shales of the Posidonia Shale type led to exceptional fossil
preservation. The high abundance of small limnic Konservat-Lager-
stätten of the Messel type in the Tertiary is dependent on Maar-type
lakes and thus on periods of high volcanic activity. It is thus of major
importance to understand the depositional environment and its
influence on the modes of fossil preservation when a genetic model of
a particular Konservat-Lagerstätte is developed.
The Eocene Pesciara di Bolca Konservat-Lagerstätte is characterized
by features similar to those found in the Malmian Solnhofen type
deposits, mainly the deposition on an extensive carbonate platform
with intra-platform depressions or basins, protected from the wash
and wave action of the open ocean by one or several thresholds
(Barthel et al., 1990; Papazzoni and Trevisani, 2006). The limestones
found in both settings are differentiated into alternation beds of pure
micritic limestone (Flinze) and usually much thinner marl beds
(Fäulen). Both settings are assumed to have been shallow water
environments, which is characteristic for most Konservat-Lagerstätten,
though deep-water settings (N200 m depth) are reported for the La
Voulte Fossil-Lagerstätte, an environment characterised by sponge
reefs equivalent to the Solnhofen type deposits (Charbonnier et al.,
2007). The environment of deposition must have been anoxic and
eventually euxinic due to the lack of bottom dwellers, except for
washed in organisms or rare currents marks. Anoxygenic conditions
enhance the preservation of organic matter primarily produced within
the water column by autotrophic organisms and also that of floating or
benthic microbial mats, these being formed by autotrophic or hetero-
trophic bacteria.
The organic matter content of the Solnhofen and the Pesciara di
Bolca limestones, however, is rather low with TOC b0.5% (Barthel et al.,
1990; Schwark et al., 1998; Papazzoni et al., 2007), whereas TOC values
of up to 15% were described for the marl intervals (Schwark et al.,1998).
Similarly low TOC values were reported for the Plattenkalke from
southern Germany (0.4–0.9%; Hückel, 1974), the Lower Cretaceous La
Huérguina Limestone Formation of Las Hoyas, Spain (0.37–1.34%;
Buatois et al., 2000) or the Late Cretaceous Hvar Facies of Hvar, Croatia
(0.73–1.23%; Swinburne and Hemleben, 1994). In accordance with
these data, exceptional fossilization in anoxic conditions does not
appear to guarantee high organic matter contents.
The low concentration of organic matter until now has restricted
the application of organic geochemical techniques to the study of the
Bolca and Solnhofen deposits. Solnhofen type deposits have been
preliminary investigated by Keupp et al. (1993) and Hefter et al. (1993)
using outcrop samples of mainly spongiolitic microbialites and in more
detail by Schwark et al. (1998) using drill core samples from well
Stoerzelmuehle. Several Upper Kimmerdigian and Lower Tithonian
strata in Franconia yield lithographic limestones and stratigraphic
misplacement of fossils has occurred frequently in the past (Fürsich
et al., 2007). It may thus be preferable to refer to the “Solnhofen type”
rather than to the Solnhofen location. The core investigated by
Schwark et al. (1998) derived from the Rennertshofen Trough, which
is separated from the Solnhofen Trough by a sponge–microbial reef
complex and thus represents a slightly different facies. The molecular
geochemical data for the Solnhofen Trough indicated a high variability in
organic matter sources (Hefter et al., 1993; Keupp et al., 1993) including
molecular fossils derived from eubacteria, cyanobacteria, archaea and
land plants. Molecular indicators of enhanced salinity as postulated for
the Solnhofen depositional environment (Barthel et al., 1990) could not
be found by Hefter et al. (1993) or Keupp et al. (1993). For the
Rennertshofen Trough adjacent to the classical Solnhofen location
(distance about 40 km) biomarker results indicated enhanced salinity
and most likely a salinity/density-stratified water column in the
platform depression surrounded by sponge/microbial reefs. Biomarker
data for samples from well Stoerzelmuehle revealed a high variability in
organic matter input from land and marine sources and intensive
273
sulphurization of biomolecules in an iron-depleted sulphur-enriched
environment.
The Pesciara Fossil-Lagerstätte, together with the neighbouring
Monte Postale, is the most outstanding fossiliferous outcrop in the
surrounding of the Bolca village, about 25 km north-east of Verona
(northern Italy; Fig. 1A). In a few square kilometres several other well-
known localities are present, such as Monte Purga, Vegroni, and
Spilecco, but only for the last one a true exposure is still maintained.
The Pesciara beds are world-wide known since the 16th century
(Sorbini, 1972) for their exceptionally preserved fossil fish, but the
extraordinary fossil content includes also snakes, birds, insects, land
plants, amber, algae, rare jellyfish, molluscs, corals, and foraminifera.
The magnificent quantity and quality of fossil fishes focussed the
attention of the scientists. Amazingly enough, not so much interest
was addressed to fix the geological features (stratigraphy, tectonics,
sedimentology, geochemistry, etc.) of the area. The age of the Pesciara
di Bolca limestone, supposed to be just across the boundary between
Early and Middle Eocene (Medizza, 1975), has been only very recently
re-assessed as late Early Eocene (Papazzoni and Trevisani, 2006).
It is the aim of the current study to investigate the organic matter
occurring in samples from the Pesciara Konservat-Lagerstätte in order
to improve the understanding of its depositional environment and to
compare this site with other Konservat-Lagerstätten of similar origin.
In this respect the bulk kerogen and the solvent-extractable bitumen
fraction will be analyzed and results compared with sedimentological
and paleocological features available for the same sample set (Papaz-
zoni and Trevisani, 2006).
2. Geological setting of the Pesciara Konservat-Lagerstätte
The Pesciara beds appear in the field as a white “spot” (a few
hundred square metres) of limestones surrounded by volcanic rocks
on the right side of Val del Fiume, about 2 km north-east of Bolca
(Fig. 1A). The strata, plunging south-easterly, are less than 20 m thick.
All the calcareous rocks of Early–Middle Eocene age in the western
Veneto area are collectively known as “Calcari nummulitici” (nummu-
litic limestones). Indeed, this name refers to different local lithos-
tratigraphical units sharing a roughly similar fossil content. Even the
Pesciara limestones do not belong to any formalized unit. The lack of
formalized units hinders so far any possible reconstruction of the
development of the carbonate platform (“Lessini Shelf” sensu Bosellini,
1989) during this time span.
A possible correlation exists between the Pesciara laminated
limestones and similar rocks cropping out in the nearby Monte Postale
(about 300 m away). Unluckily, due to the widespread occurrence of
volcanic and volcanoclastic rocks and to the tectonic displacement of
the sedimentary beds, the relationships between these localities are
still unclear. This will be matter for a forthcoming paper.
Bolca lays East of the Castelvero Line, a tectonic element running
NNW–SSE on the right side of the Val d'Alpone. This fault complex
determined and controlled the volcano-tectonic and paleoenviron-
mental evolution of the Lessini area during the Late Paleocene–Middle
Eocene. Then, the Castelvero Line acted as a tectonic threshold sepa-
rating a western sector with thin and discontinuous volcanic products
from an eastern sector where the major part of volcanic (basaltic) rocks
accumulated during this time span.
During the same interval, there were several pulses of activity
involving the Castelvero Line, generating a stepwise subsidence of the
eastern sector, which became a tectonic low known as Alpone-Agno
semigraben (Barbieri et al., 1982, 1991). Here volcanic rocks accumu-
lated, intercalated with marine carbonates during the volcano-
tectonic stasis (Barbieri, 1972; De Zanche and Conterno, 1972). The
extensive tectonic movements, mainly documented near the Castel-
vero Line, were discontinuous and coincident with the main volcanic
activity. Six phases were recognized by Barbieri et al. (1991) between
the Late Paleocene and the Middle Eocene.
274 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285
Fig. 1. Location map (A) and stratigraphic column (B) of the Pesciara Section (simplified after Papazzoni and Trevisani, 2006).
The Monte Postale and Pesciara carbonate deposition probably
occurred during the interval between the third and the fourth volcanic
phase of Barbieri et al. (1991).
The fair continuity of the carbonate deposits East and West of the
Castelvero Line suggests that the tectonic accommodation repeatedly
produced East of the fault was quickly filled in by the volcanic products.
Within the Alpone-Agno semigraben, the sediments of Paleocene–
Eocene age were subjected to brittle deformation, subdivided into
separate blocks by plane and subparallel faults in a generally extensive
setting. The blocks were tilted and moved with a domino-style
arrangement (Barbieri and Zampieri, 1992; Zampieri, 1992, 1995).
The Bolca area belongs to a tectonic low bordered on the West by
the Castelvero Line faults, running NNW–SSE, and on the East by the
Monte Postale fault (Barbieri and Medizza, 1969; Dal Degan and
Barbieri, 2003), a subvertical line nearly parallel to the Castelvero Line.
This structure probably created the space for the accommodation of
the carbonate sediments during the Eocene.
3. Investigated material
Most of the spectacular biota recovered in the classic Pesciara
Section of Bolca derives from fine-grained and evenly laminated
limestones, up to 1 m thick, organized in five distinct major levels (L1
to L5; Papazzoni and Trevisani, 2006). These productive layers are
intercalated with storm-induced coarse-grained limestones rich in
molluscs and foraminifera, but devoid of any fish remnants (Fig. 1B).
Four main microfacies types were recognized by Papazzoni and
Trevisani (2006). The M microfacies characterizes autochthonous
micritic limestones (levels L1 to L5) rich in fish and plants but with few
recognizable bioclasts. A further subdivision in three subunits (M1, M2
and M3 microfacies) was attempted on the basis of the presence of
black laminae (M1), white sparitic laminae (M2) or of the absence of
any lamination (M3). The F microfacies typically consists of biocalcar-
enite–biocalcirudites containing abundant resedimented benthic
organisms, mainly foraminifera and molluscs, indicative of a very
shallow environment. This facies often occurs in alternation with the
M microfacies. The B microfacies represents a calcareous-siliceous
breccia with extraclasts present in the lower part of the section.
Finally, the N microfacies, limited to a single submittal sample, typifies
biocalcarenites–biocalcirudites with an autochthonous association of
nummulites and assilinas.
Papazzoni and Trevisani (2006) recently proposed a depositional
model for the Pesciara Section, referring to a shallow basin with
restricted circulation (“lagoon”) and anoxic conditions prevailing in
stagnant bottom waters.
The material used in this work comes from the recent sampling of
Papazzoni and Trevisani (2006) both on the surface and into tunnels
opened to extract the fossil fishes. Either laminated or the coarse-
grained calcareous levels were selected (Table 1). As regards the
former, levels L1 (samples 0201 and 0202), L2 (sample 0207) and L3
(sample 0214) have been analysed. They characterize the M micro-
facies. Within the coarse-grained beds (F microfacies), we used
 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285 275

Table 1
Stratigraphic location and main features of levels investigated for geochemistry

Sample no. Short description Position within or m above datum Microfacies (⁎) Notes
relative to fish levels
0223 Wackestone with small foraminifera. Above L4 17.00 M3 –
0220 Packstone–rudstone with bivalves and alveolinas. Above L4 15.10 F –
0218 Faintly-laminated, marly wackestone. Under L4 (see note) 13.75 M3 Nucleus of the slump involving L4.
0216 Non-laminated, marly wackestone. Some coarser laminae Between L3 and L4 10.15 M3-F –
with alveolinas intercalated.
0215 Non-laminated to faintly-laminated, marly wackestone. Between L3 and L4 9.25 M3 In vicinity to a basaltic dyke.
0214 Laminated limestone. Some coarser laminae with miliolids L3 7.85 M2 Fish are often deformed in this level.
intercalated.
0212 Wackestone with miliolids and alveolinas, in places faintly Between L2 and L3 7.00 F –
laminated.
0207 Laminated limestone. L2 6.35 M1 –
0206 Grainstone with abundant miliolids. Intercalated within L2 5.90 F –
0204 Packstone with alveolinas. Between L1 and L2 3.65 F –
0203 Bioclastic, brecciated packstone with alveolinas. Many clasts Just over the top of L1 2.70 B –
are silicified.
0202 Clayey-silty marl, evenly laminated. L1 1.00 M1 –
0201 Evenly-laminated limestone. L1 0.50 M1 –

⁎ refers to microfacies types described by Papazzoni and Trevisani (2006) and briefly summarized in the text.

material from the massive biocalcarenite–biocalcirudites (samples
0204, 0212 and 0220), from the centimetre-thick bioclastic levels
(samples 0206 and 0216) and from those levels revealing either no
lamination or a faint lamination (samples 0215, 0218 and 0223).
Finally, even the basal calcareous-siliceous breccia rich in benthic
fossils (sample 0203; B microfacies) has been investigated.
3.1. Analytical methods
For all sampled levels, total carbon, nitrogen content, organic carbon
content and stable isotopic analyses of organic C were determined in
Bologna, Italy. After this first set of analyses, material from the same
levels was prepared for kerogen analyses and specific biomarker iden-
tification in Cologne, Germany.
Total carbon and nitrogen were determined using a FISONS NA2000
Elemental Analyzer (EA). The organic carbon contents were determined
using the same instrument after removal of the carbonate fraction by
dissolution in 1.5 normal HCl. Stable isotopic analyses of organic C were
carried out by using a FINNIGAN Delta Plus mass spectrometer, which
was directly coupled to the FISONS NA2000 EA by means of a CONFLO
interface. The IAEA standard NBS19 was used as calibration material for
carbon. Uncertainties are usually lower than ±0.2‰, as determined from
routine replicate measurements of a reference sample. Stable isotopic
data are expressed in the conventional delta (δ) notation in which the
13 12
C/ C isotopic ratios are reported relative to the international VPDB
standard.
Homogenized, finely crushed and ground samples were decalcified
with 10% HCl and washed till neutral. The carbonate content was
calculated by difference between sample material subjected to HCl
treatment and residual fraction remaining thereafter. The decalcified
sample powder was then subjected to elemental analysis and Rock-Eval
analysis. Elemental analysis was conducted for total organic carbon of
the decalcified sample TOCcf and total sulfur of the decalcified samples
TScf using a LECO CS225 Elemental analyzer.
Rock-Eval analysis was performed according to the method
described by Espitalié et al. (1977) and Bordenave et al. (1993) with
a VINCI Rock-Eval-II Analyser. S1, S2 and Tmax values were measured
and corresponding HI, OI and PI values calculated. For details of
procedure and interpretation see Lüniger and Schwark (2002).
Bitumen was extracted from bulk rock by accelerated solvent
extraction (DIONEX ASE 200) with dichloromethane (DCM) at 75 and
120 °C and 50 bar pressure, whereafter the extracts were combined.
Elemental sulfur was precipitated from the raw extract by addition of
activated copper foil. After filtration samples were taken to dryness
and extract yields determined gravimetrically. The low extract yields
of commonly 0.5 to 2 mg prevented sophisticated compound class
separation by MPLC as commonly applied (Schwark et al., 1998). Total
extracts were thus derivatized with bis-silyl-trifluoracetamid (BSTFA)
to make polar functionalized lipids amenable to GC/MS analyses.
GC/MS analysis of derivatized extracts was carried out using a HP
5890 Series II gas chromatograph coupled to a HP 5989 single
quadrupole mass spectrometer. A 50 m long fused silica column (HP 5)
with an internal diameter of 0.25 mm, coated with 5% chemically
bonded phenyl-polysiloxane (0.25 µm) was used with helium as
carrier gas at a constant flow rate of 1.0 ml/min. Injection was done in
the splitless mode at a temperature of 300 °C. Following an isothermal
period of 2 min, the GC oven temperature was programmed from 70 to
140 °C at a rate of 10 °C/min followed by a second gradient from 140 to
320 °C at 3 °C/min. The mass spectrometer operated in EI mode at
70 eV with a scan range from m/z = 50 to 600 for identification of
individual compounds. Data acquisition and processing was per-
formed using a HP MS-ChemStation data system. Peak identification
was based on retention times and on comparison of mass spectra with
those of the system library and published spectra.
4. Results
4.1. Carbonate content
The amount of carbonate was independently assessed by the loss
upon HCl treatment and by the difference between total carbon (TC) and
organic carbon (TOC) yielding the total inorganic carbon (TIC). Under the
assumption that the carbonate phase is calcite, TIC ⁎ 8.33 yields the
carbonate content. Elemental data generated in Italy (CNR-ISMAR in
Bologna) are listed in Table 2 and agree well (R2 = 0.9877) with the
carbonate content determined by HCl dissolution in Cologne (Table 3)
though the carbonate determination using the TIC systematically
overestimates the actual concentration. This must be due to calibration
problems with carbonate rich samples as no indication of a different
carbonate phase and thus lower stoichometry factors is evident.
Except for sample 0203, which is a silicified breccia with a
carbonate content of less than 15%, most other samples contain N90%
carbonate, as also confirmed by X-ray analyses. Lower carbonate
values of 82 and 84.5% were encountered in samples 0202 and 0206,
respectively. Sample 0202 is a dark-coloured marl bed from the main
fish-bearing level L1 in the Pesciara Section (Papazzoni and Trevisani,
2006), where the non-carbonate fraction is assumed to be clay, pyrite
and abundant organic matter (Table 2). Sample 0206 does not contain
276 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285

Table 2
Organic geochemical data for raw samples from the Eocene Pesciara Section

Sample Lithology TN (%) TC TOC (%) TIC (%) δ13C (‰ VPDB) TOC/TN Extract (ppm) Extract (mg/gTOC) Carbonate (%)
0223 Calcarenite 0.010 12.98 0.46 12.52 −25.6 45.3 64 14.0 104.3
0220 Calcarenite 0.005 13.02 0.19 12.83 −26.0 34.2 58 31.0 106.9
0218 Calcarenite 0.009 13.13 0.36 12.77 −26.0 41.2 50 13.8 106.3
0216 Bioclasts 0.009 13.05 0.33 12.72 −26.3 36.9 81 24.3 105.9
0215 Calcarenite 0.014 12.27 0.55 11.72 −24.0 39.4 72 13.1 97.7
0214 Laminated micrite 0.007 12.98 0.35 12.63 −25.5 47.5 68 19.4 105.2
0212 Calcarenite 0.006 12.84 0.24 12.60 −26.3 37.4 24 10.1 105.0
0207 Laminated micrite 0.011 12.78 0.49 12.29 −24.7 45.4 85 17.4 102.4
0206 Calcarenite layer 0.005 11.04 0.16 10.88 −25.0 32.5 14 8.8 90.7
0204 Calcarenite 0.004 12.78 0.16 12.63 −26.7 37.5 3 1.8 105.2
0203 Siliceous breccia 0.005 1.30 0.21 1.09 −26.3 44.3 32 15.5 9.1
0202 Laminated micrite 0.195 18.04 8.60 9.44 −24.2 44.0 1486 17.3 78.6
0201 Laminated micrite 0.012 12.43 0.48 11.95 −25.6 38.6 85 17.6 99.5
Average 0.023 12.20 0.97 11.24 −25.6 40.3 163 15.7 93.6

abundant clay and organic matter indicating that most of the non-
carbonate fraction is due to silicification.
4.2. Organic carbon, total nitrogen, and total sulfur content
The organic carbon contents of samples from the Pesciara Section
are low, with values between 0.16 and 0.55% TOC, except for sample
0202 showing an exceptional value of 8.60% TOC. The total nitrogen
concentrations closely follow the TOC concentrations (Table 2). The C/
N ratios of the organic matter varied between 33 and 48, with a mean
42.8 value for productive layers and a mean 37.2 value for bioclastic
layers (Table 2). For samples of this age and diagenetic stage this does
not allow for a differentiation of marine versus terrigenous matter
prevalence (Tyson, 1995). The low TOC values preclude a detailed
interpretation of environmental change across the profile investi-
gated. This compares well to the Malmian carbonates of the
Franconian Alb in Germany, where very low TOC concentrations
prevailed in the Solnhofen location but enhanced TOC contents were
noted in samples from well Stoerzelmuehle. The low concentrations of
TOC in the finely laminated carbonates from Solnhofen are assumed to
be at least partially due to post-sedimentary oxidation and loss of
organic matter (Barthel et al., 1990; Schwark et al., 1998). In analogy it
may be assumed that the fish-bearing levels L2 to L4 originally
contained higher concentrations of organic matter but lost a notable
proportion upon later weathering. This is supported by the low degree
of correlation between TOCcf and TScf values of decalcified samples
(Table 3). The sulfur content of decalcified samples is very high with
values up to 56% in sample 0216, due to intensive pyritisation. The fact
that at least some sedimentary intervals of both Konservat-Lager-
stätten still bear relicts of concentrations of primary organic matter
content indicates deposition under anoxic stagnant water conditions.
4.3. Organic carbon isotopic composition
The δ13C isotopic composition of the Pesciara samples ranges
between −24.0‰ and −26.7‰, thus indicating an origin from C3-
photosynthesis by aquatic or terrestrial organisms. Values of bioclastic
limestones (mean −26.1‰) are notably lighter than those of the
productive layers (mean −25.2‰).
4.4. Rock-Eval analyses
Investigation of sedimentary organic matter by Rock-Eval provides
information on the type of organic matter accumulated, the thermal
maturity stage of the kerogen, and indicates the presence of migrated
bitumen or impregnation (Espitalié et al., 1977; Peters, 1986;
Bordenave et al., 1993; Lüniger and Schwark, 2002). Interpretation
of Rock-Eval data is only recommended, if the TOC value of the
sediments to be investigated is N0.5% TOCcf (Espitalié et al., 1977;
Peters, 1986; Bordenave et al., 1993; Langford and Blanc-Valleron,
1990). Insufficient amount of organic matter leads to erroneous results
due to unpredictable mineral matrix effects, low signal intensities and
associated unacceptably low signal to noise ratios. Given these
limitations, only but one of the samples from the Bolca location
would have been suitable for analyses. The decalcified samples
subjected to the Rock-Eval analyses with the exception of the breccia
(Table 3) all fulfill the requirements for Rock-Eval analyses, given that
TOC concentrations of the residual fractions average 12.2%. The
kerogen concentration in the residual fraction is high, with an average
of 55 mg hydrocarbons per gram of rock (Table 3). Hydrogen index
(HI) values for the Pesciara Section sediments vary between 237 and
626 (mg HC/g TOC) as shown in Table 3. The low HI values of the
breccia sample are due to the lack of indigenous kerogen, most of the

Table 3
Organic geochemical data for decalcified samples from the Eocene Pesciara Section

Sample Lithology HCl soluble (%) TOC (%) S (%) Tmax (°C) S1 S2 S3 PI HI OI
residual residual (mg HC/g rock) (mg HC/g rock) (mg CO2/g rock) (mg HC/g TOC) (mg CO2/g TOC)
0223 Calcarenite 98.4 24.80 12.45 407 8.1 108.7 10.0 0.07 438 40
0220 Calcarenite 99.4 20.62 14.83 405 3.8 72.36 8.5 0.05 351 41
0218 Calcarenite 98.8 18.51 19.13 406 7.4 93.42 6.4 0.07 505 34
0216 Bioclasts 97.8 6.67 56.76 409 1.8 23.60 3.4 0.07 354 51
0215 Calcarenite 97.9 12.34 19.36 406 6.8 39.33 2.5 0.15 319 20
0214 Laminated micrite 98.9 17.35 10.29 407 8.6 108.6 3.1 0.07 626 18
0212 Calcarenite 99.5 11.32 1.44 418 2.0 41.36 3.6 0.05 365 32
0207 Laminated micrite 98.6 21.30 3.33 412 10.1 120.1 3.7 0.08 564 17
0206 Calcarenite layer 84.5 0.91 0.33 415 0.2 2.16 0.5 0.08 237 55
0204 Calcarenite 98.7 1.60 0.10 424 0.6 5.55 1.3 0.09 346 82
0203 Siliceous breccia 14.7 0.16 0.00 384 0.1 0.03 0.1 0.79 – 32
0202 Laminated micrite 82.0 16.35 8.60 408 9.5 81.00 5.3 0.11 495 32
0201 Laminated micrite 93.3 6.99 12.46 400 4.8 25.60 1.2 0.16 366 17
Average 89.4 12.22 12.24 408 4.9 55.53 3.8 0.14 414 36
L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285 277

organic matter present being a product of impregnation from adjacent

strata. This is to be recognized by the exceptionally high production
index (PI) reaching a value of 0.79 (Table 3). In general the PI values are
very low (b0.1) or low in samples 0201, 0202, and 0215 (b0.15), which
is indicative of the low thermal maturity of the organic matter. This is
supported by the low Tmax values of an average 408 °C, except for the
breccia sample where the low TOC content leads to erroneous Tmax
determination. Higher Tmax values are encountered in samples 0204
to 0212, which might indicate the presence of more refractory organic
matter. The Rock-Eval data show no evidence for enhanced thermal
maturation of the organic matter due to the volcanics emplaced
within the Pesciara Section.
The oxygen content of the organic matter (OI) serves as a proxy for
the amount of terrigenous matter being present. The OI values of
samples from the Pesciara site average 36 (mg CO2/gTOC) with
elevated values noted for samples 0204 and 0206 that already showed
higher proportions of non-marine refractory material by their
corresponding Tmax values. A higher OI value also occurs with the
bioclastic calcarenite of sample 0216, remarkable by its exceptional
degree of pyritization.
HI versus OI values or HI versus Tmax values allow to classify the
kerogen in the Pesciara sediments as marine type II of low thermal
maturity (Fig. 2). The mineral matrix effects (Langford and Blanc-
Valleron, 1990; Lüniger and Schwark, 2002) affecting raw samples to a
high degree are almost absent in the decalcified Pesciara samples. This
leads to a regression line with an intercept close to the origin (Fig. 2)
indicative of no retardation of the pyrolizate. Rock-Eval data on
decalcified limestones clearly indicate that despite of the low
concentrations of total organic matter, the quality of preservation
was high in the Pesciara basin and favored the development of a true
Konservat-Lagerstätte.

4.5. Bitumen content

The amount of extractable bitumen is closely correlated with the

TOC values (R2 = 0.988) and varies between 3 and 1486 ppm (Table 2). If
normalized to TOC content the low values of on average 15.6 (mg Ext/
gTOC) indicate an immature stage of kerogen evolution. This is in
agreement with PI and Tmax values determined in Rock-Eval analyses.
The low absolute amounts of bitumen prevented a compound class
separation by liquid chromatography and thus total extracts were
analyzed by GC/MS for the presence of source and environment
characteristic biomarker molecules. In recognition of the permeability
of the carbonate rocks and the mobility of bituminous fluids in the pore
space of the subsurface care has to be taken to make sure that the
bitumen is of autochthonous nature when organic facies interpretation
is envisaged (Peters et al., 2005). The low PI values of most samples and
the high variability in extract yields and composition argue against an
impregnation of the pore space by a homogeneous allochthonous fluid.
Except for few samples (see below) the bitumen composition will thus
be indicative of environmental change across the Pesciara profile.

4.6. Molecular composition

Organisms biosynthesize a large variety of different molecules in

response to the environmental demands prevailing. Many of the
characteristic biomolecules can be preserved with minor or no alteration

Fig. 2. Rock-Eval data for source and maturity identification. A) A pseudo van Krevelen
diagram depicts samples as type II kerogen of low maturity, with some degradative
alteration and admixture of terrigenous material. B) The HI versus Tmax diagram
confirms a type II kerogen of low maturity that has been affected by secondary
alteration. C) An improved kerogen classification diagram minimized the mineral
matrix effects yielding an averaged HI value of 495 (mg HC/g TOC) calculated from the
slope of the regression line.
278 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285

Table 4 ubiquitous isoprenoidal alkanes phytane, pristane, norpristane and

Selected biomarker data for samples from the Eocene Pesciara Section smaller analogues, a suite of saturated steranes with different degree of
Sample Lithology Pri/Phy Phy/ Short/long n-C16/ HBI20/ HBI25/29 alkylation at the C24-position and a series of hopanes and hopenes.
n-C18 n-alkanes n-C17 n-C17 Functionalized lipids are mainly represented by carboxylic acids,
0223 Calcarenite 0.87 0.55 4.14 1.68 0.39 2.80 whereas alcohols were not determined in notable concentrations. The
0220 Calcarenite 0.95 0.39 5.39 2.38 0.26 4.05 fatty acids in all but one sample are exclusively medium-chain
0218 Calcarenite 0.68 0.82 2.78 1.61 0.48 1.98
homologues in the C14 to C18 range, predominantly occurring as n-
0216 Bioclasts 0.91 0.52 7.89 2.29 0.48 2.33
0215 Calcarenite 0.96 0.75 2.01 1.94 0.77 1.97 fatty acids with subordinate amounts of branched and unsaturated
0214 Laminated micrite 0.87 0.58 6.14 1.60 0.51 2.35 fatty acids (Fig. 4).
0212 Calcarenite 0.86 0.51 3.77 1.30 0.38 2.13 The only exception from this pattern is given by sample 0202,
0207 Laminated micrite 0.65 1.73 1.15 0.95 2.86 4.44 which is the most TOC-rich and unaltered. Here a suite of long-chain
0206 Calcarenite layer 0.64 0.82 1.54 0.82 2.73 8.71
0204 Calcarenite 0.90 0.58 3.44 0.88 0.31 0.79
fatty acids extending up to the n-C32 homologue is present (Fig. 4). The
0203 Siliceous breccia 0.77 0.59 2.10 0.82 0.03 2.84 carbon preference index of these n-carboxylic acids attests to the low
0202 Laminated micrite 0.55 3.25 0.73 0.81 2.04 5.86 thermal maturity of the extractable bitumen and clearly indicates an
0201 Laminated micrite 0.65 1.57 1.99 1.33 1.10 3.44 origin from cuticular waxes of land plants.
Average 0.87 0.59 4.59 1.42 0.95 2.52
Cyclic biomarkers occurred in low concentrations close to the
detection/identification limit in most samples. The cyclic biomarker
distribution is dominated by triterpenoidal steranes, hopanes and
hopenes. Functionalized triterpenoids are restricted to hopanoic acids.
in sediments and these geomolecules provide evidence on the Despite of the low maturity of the samples no sterenes, steradienes or
organisms that once thrived in the environment of deposition. their respective rearranged counterparts were detected. The hopanoid
Molecules that are indicative of a specific biological precursor are called distribution was dominated by ββ-hopanes and contained diploptene
biomarkers or chemofossils and serve in the reconstruction of organic but no hop(17,21)enes usually abundant in low maturity samples of
facies (Table 4). For a more detailed introduction into the principles of comparable organic facies, e.g. the Solnhofen type limestone (Schwark
organic geochemistry the unfamiliar reader is referred to Peters et al. et al., 1998). Though not quantified in detail due to the low extract
(2005), Killops and Killops (2005), and Brocks and Summons (2007). yields, the proportion of steroids outcompetes that of hopanoids
The distribution of biological markers found in the Pesciara samples revealing a dominance of algal over eubacterial/cyanobacterial lipid
is illustrated by four typical and representative gas chromatograms sources. The sterane distribution shows higher abundances of the C27
shown in Fig. 3. The hydrocarbon components identified comprise a and C29 analogues. The former represent an algal input, in particular
series of n-alkanes ranging from n-C12 to n-C34, a series of highly from rhodophytes, the latter may derive from green or brown algae but
branched isoprenoids (HBI) with 20, 25, 29 and 30 carbon atoms, the also from land plants (Killops and Killops, 2005; Peters et al., 2005). The

Fig. 3. GC/MS mass fragmentograms (m/z 85) of four characteristic samples from the Pesciara Section, revealing the distribution of aliphatic hydrocarbons.
 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285
low concentrations of C28 steroids stand in contrast to their prefe-
rential biosynthesis by diatoms and prymnesiophytes (Peters et al.,
2005), both algal classes assumed to be abundant in the Pesciara basin.
Sample 0202 from the base of the section, giving the highest
bitumen yield was characterized as having received a notable input of
land plant derived alkyl lipids and in addition also showed triterpe-
noids of the oleanene type, characteristic of angiosperm plants. No
aliphatic or aromatic diterpenoids, indicative of gymnosperm input
into the Pesciara basin were detected in the total extract fractions.
5. Discussion
The organic geochemical data determined for the bulk kerogen and
for the extractable biomarkers allows addressing the following issues:
i) identification of marine algal and microbial groups contributing to
the organic matter, ii) identification of terrigenous input into the
Pesciara basin, iii) the redox potential prevailing in the sediments, iv)
assessment of the salinity in the Pesciara basin and v) recognition of
stratigraphic variability in environmental conditions.
5.1. Marine organic matter
The biomarker distribution of most samples is dominated by HBI
compounds that are biosynthesized by a variety of diatoms (Yon et al.,
1982; Rowland and Robson, 1990; Sinninghe Damsté et al., 2004). The
relative distribution of HBI in diatoms is dependent on species as well
as growing conditions but a differentiation of diatom type or
environment based on relative abundance of individual HBI is not
yet possible (Peters et al., 2005). Whereas C20, C25 and C30 HBI have
been described frequently and in rare occasions C35 HBI have been
found (Peters et al., 2005), a C29 analogue as inferred from interpreta-
Fig. 4. GC/MS mass fragmentograms (m/z 117) of four characteristic samples from the Pesciara Section, revealing the distribution of carboxylic acids.
279
tion of elution time and mass spectral fragmentation pattern to occur
in the Pesciara extracts in notable concentrations (Fig. 3), so far has not
been reported.
Short-chain n-alkanes preferentially derive from aquatic primary
producers, in particular algae and cyanophytes but may also be
attributed to heterotrophic bacteria (Peters et al., 2005). Their do-
minance in all samples documents the predominantly marine organic
matter sources in the Pesciara Section. Except for sample 0202 all
carboxylic acid fractions are dominated by saturated short-chain fatty
acids (Fig. 4) again indicative of marine autotrophs but also hetero-
trophic bacteria. Iso- and antiso-C15 and C17 fatty acids, which are
indicative of bacterial sources, e.g. sulfate reducers, occur in minute
amounts only in sample 0202 and generally lack in the remaining
samples thus emphasizing a surprisingly low abundance of bacterial
biomass, as already indicated by the low hopanoid versus steroid
concentrations.
5.2. Terrigenous organic matter
The bulk geochemical data revealed a low input of terrigenous
organic matter, which is in agreement with the overwhelmingly pure
carbonate lithology that does not allow for large quantities of
terrigenous influx. The HI and OI values from Rock-Eval analyses
indicate a marine organic matter with variable degree of oxidative
degradation. The lipid composition, however, indicates terrigenous
influx, especially in the lower section and here, in particular in sample
0202 (Figs. 3 and 4). Long chain n-alkanes and carboxylic acids are well-
known and reliable indicators of land plant waxes (Killops and Killops,
2005) and are clearly recognizable in sample 0202. Plant waxes in
contrast to woody plant material can reach the marine or limnic
environment by eolian transport (Gagosian and Peltzer, 1986; Gagosian
280 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285

et al., 1987; Lüniger and Schwark, 2002). Therefore, they are common in
marine settings receiving little or no fluviatile input (Rontani and
Volkman, 2005). The wax lipids then contribute only a minor proportion
to the bulk kerogen but occur exclusively in solvent-extractable form.
Because of this and because of their recalcitrance (Peters et al., 2005;
Marschner et al., 2008) they are overrepresented in the solvent extracts
of the kerogen lean-samples. The cyclic biomarkers indicate input of
angiosperm lipids whereas gymnosperm lipids are not detectable, but
Trevisani et al. (2005, Table 2) reported pollens of Gymmosperms,
Auracariaceae (genus Araucariacites), plus some spores of Bryophyta
(genus Stereisporites) and Pteridophyta (genera Gleichenidiites, Leiotri-
letes, Cicatricosisporites, Echinatisporis), all from L1. This discrepancy
may be explained by the low amount of free lipids in spores and pollen,
which thus do not contribute to the biomarker yield of the sediments.
Wind transported plant wax rich in angiosperm triterpenoids, however,
contribute significantly to the free lipids but do not leave microscopically
identifiable objects. A terrigenous influx agrees well with plant
macrofossils (Massalongo, 1859a,b; Papazzoni and Trevisani, 2006)
though the biomarkers in the pure carbonates may preferentially
indicate eolian influx, whereas the macrofossil evidence and the high
abundance of terrigenous lipids in sample 0202 may originate from
fluviatile transportation.
5.3. Redox regime
Preservation of biomarker lipids and primary composition of
biomolecules synthesized by organisms occupying a given environment
highly depend on the oxygen availability or redox regime. A classical
indicator of redox conditions is given by the breakdown of chlorophyll,
ubiquitous in phototrophs, leading to either phytane under reducing or
pristane under oxidizing conditions (Powell and McKirdy, 1973; Didyk
et al., 1978). The pristane/phytane ratio though it may be affected by
various factors (ten Haven et al., 1985; Frimmel et al., 2004; Peters et al.,
2005) indicates reducing conditions by values b1.0. According to this
threshold value all samples from the Pesciara site were deposited under
reducing conditions, with lower Eh values in the lower and higher Eh
values in the upper part of the section (Fig. 5). The molecular redox
indication corresponds to the high preservation potential documented

Fig. 5. Trends in biomarker distribution along the Pesciara profile: A) pristane/phytane ratio, B) phytane/n-C18 ratio, C) hydrogen index HI (mg HC/g TOC), D) δ13Corg (‰), E) short/
long-chain n-alkanes, F) n-C16/n-C17 ratio, G) HBI20/n-C17 ratio, H) HBI25/HBI29 ratio. Open symbols represent samples 0203 and 0204, both affected by impregnation.
 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285
by the kerogen Rock-Eval data though the latter are not suitable for
differentiation of redox gradients across the profile (Fig. 5). In a similar
fashion, the relative proportions of phytane and octadecane find
application as redox proxy. The higher phytane/n-C18 ratio in the
lower part of the Pesciara Section and the trend to lower values in the
upper part confirm the Eh assessment based on the pristane/phytane
ratio. The environment of deposition is thus interpreted as having been
severely oxygen depleted (anoxic) though most likely not enriched with
reduced sulphur species within the water column (euxinic). This is
inferred from the lack of sulphurized biomarkers, commonly formed
during early stage of diagenesis in comparable settings, e.g. the
Solnhofen type deposits (Schwark et al., 1998) and from the absence of
aromatic carotenoids and their derivatives. In shallow stratified water
columns with euxinic bottom water microbial communities bearing
green sulphur bacteria (chloriobiaceae) thrive within the photic zone
(Summons and Powell, 1986; Schwark and Püttmann, 1990; Grice et al.,
1996a). Whereas aryl isoprenoids are common and diagnostic in the
Fossil-Lagerstätte of the Toarcian Posidonia Shale (Schwark and Frimmel,
2004), they were not detected in the Jurassic limestones of the
Solnhofen type (Schwark et al., 1998) and in the Pesciara Section
occurred in trace amounts exclusively in sample 0202. Chlorobiaceae
not only utilize specific accessory pigments of the renieratene
carotenoid type but also employ bacteriochlorophyll for photosynthesis
that upon early diagenesis yields butyl- and isobutyl maleimides instead
of the ubiquitous methyl-etyhlmaleimides (Grice et al., 1996b). Whereas
the latter were present in polar lipids from the Pesciara site the former,
indicative of photic zone euxinia could not be detected. The molecular
signatures thus indicate that the environment of deposition at the
Pesciara Section was strongly anoxic but did not reach the euxinic stage,
except for short intervals during deposition of the L1 level.
5.4. Paleosalinity
A variety of paleosalinity indicators based on molecular composi-
tion of extractable bitumens have been established (ten Haven et al.,
1985; Peters et al., 2005). Enhanced salinity environments do support
highly variable microbial communities depending on the degree of
salinity and other environmental variables. Consequently, a large
variety of molecular indicators of enhanced salinity have been
postulated (for summary see e.g. ten Haven et al., 1985; de Leeuw
and Sinnighe Damsté, 1990; Schwark et al., 1998; Peters et al., 2005). In
many cases microbial communities that are able to cope with
enhanced salinity environments also are able to survive in other
hostile, e.g. euxinic environments. Microbial communities in many
cases thrive at interface layers in the water column, which can be
haloclines, thermoclines, pycnoclines or chemoclines (oxic/anoxic
interfaces) or combinations thereof. Microbial communities living at
such interfaces in stratified water bodies are difficult to distinguish by
biomarkers. As a consequence no single biomarker ratio is suitable for
distinction of enhanced salinity but a variety of parameters should be
applied to increase reliability of interpretation.
A biomarker often applied as paleosalinity indicator is the triterpe-
noid gammacerane (ten Haven et al., 1985; Schwark et al., 1998;
Stephens and Carroll, 1999) that derives from tetrahymanol, a
compound biosynthesized by bacteriovorous ciliates. Gammacerane
has also been reported from non-hypersaline settings and may in
general be an indicator for strictly stratified water bodies (Sinninghe
Damsté et al., 1995), a situation often coinciding with salinity strati-
fication. Gammacerane was not detected in significant amounts in the
total extracts from the Pesciara Section.
Commonly very low pristane/phytane ratios of b0.5 have been
associated with hypersalinity (ten Haven et al., 1985, 1987; Barbé et al.,
1990; Schwark et al., 1998), though it is clear that this ratio is also very
susceptible to the redox regime. The pristane/phytane ratio in the
Pesciara sediments analyzed varies between 0.55 and 1.0 and thus
indicates highly reducing conditions as stated above. In order to indicate
281
hypersalinity empirically a value of 0.3 has been established (ten Haven
et al., 1985), which is not reached in the Pesciara Section. In hypersaline
environments the diagenesis of steroids is supposed to follow a different
route, leading to high concentrations of ββ-steranes at low maturity
levels (de Leeuw and Sinninghe Damsté, 1990). The sterane distribution
of the Pesciara samples is dominated by C27 to C29ααα steranes with the
biological 24R configuration, thus showing no indication of enhanced
salinity. The distribution of alkylated chromans has been applied for
identification of paleosalinity levels (Sinninghe Damsté et al., 1987, 1993;
Schwark and Püttmann, 1990; Schwark et al., 1998) but has been
questioned by Li et al. (1995). No alkylated chromans were detected in the
Pesciara sediments and thus no salinity assessment is possible based on
their relative distribution. In hypersaline sulfur-enriched environments
early incorporation of reduced sulfur species is common and allows for
salinity discrimination based on a variety of thiophene and thiolane
compounds (Sinninghe Damsté et al., 1989, 1990; Schwark et al., 1998). In
the Pesciara samples, no organic sulfur compounds were detected and
thus no paleosalinity information could be derived. In summary all
common molecular paleosalinity indicators either showed no values
indicative of enhanced salinity or the indicator compounds were not
present. This multiple evidence strongly implies that the salinity during
deposition of the Pesciara sediments was not enhanced and did not
partake in forming the Konservat-Lagerstätte. A different picture was
obtained for the Solnhofen limestones where a variety of molecular
indicators indicated higher salinity during deposition, including presence
of gammacerane, organic sulfur compounds, alkylated chromans,
exceptionally low pristane/phytane ratios and high proportions of
ββ-steranes and earlier diagenetic intermediates (Schwark et al., 1998).
5.5. Stratigraphic variability
In order to assess the stratigraphic variability along the profile using
biomarkers it is mandatory that these compounds are preserved in situ
and no migration or impregnation occurred. This pre-assumption is not
guaranteed for samples 0203 and 0204 which are prone to dissolution
and migration of aqueous and hydrocarbon fluids. Upon migration of
aliphatic hydrocarbons fractionation occurs that will lead to a
preferential retardation of branched compound in the source interval
and an enrichment of n-alkanes in the impregnated pore network of the
host rock (Leythaeuser and Schwarzkopf, 1986). Samples 0203 and 0204
from the Pesciara Section do exhibit impregnation features (Table 3,
Fig. 5) and thus are excluded from most of the following discussion as
the autochthony of the biomarkers is questionable.
Along the profile a notable change occurs at about 7 m above datum,
i.e. between samples 0207 and 0212. The lower part of the section is
characterized by higher proportions of marly, laminated limestones
lacking benthic fauna. The upper part of the section is characterized by a
dominance of biocalcarenites and biocalcirudites with abundant benthic
element (Papazzoni and Trevisani, 2006). This points towards an
increase in basin ventilation and higher oxygen availability in the
upper section and more restricted and anoxic conditions in the lower
section.
The pristane/phytane ratio is a well established indicator of redox
conditions (Powell and McKirdy, 1973; Didyk et al., 1978) that depends
on the differentiation of phytol degradation under reducing versus
oxidizing conditions. Oxygen availability leads to formation of
phytenic acid which is consecutively decarboxylated thus yielding
pristane, an isoprenoid that has lost one carbon atom when compared
to its biological precursor phytol. Care must be exercised in the
interpretation of pristane/phytane ratios, if one of the components is
not originating from chlorophyll breakdown but derived from other
sources (ten Haven et al., 1987; Frimmel et al., 2004). In particular
tocopherol derived from marine algae may increase the relative
proportion of pristane (Goossens et al., 1984; Frimmel et al., 2004),
whereas phytane may originate from breakdown of bisphytanes (ten
Haven et al., 1987). No indication of additional sources for pristane and
282 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285
phytane could be detected in the Pesciara Section. The ratio may thus
be taken to reflect changes in Eh condition during sedimentation.
A marked shift occurs at 7 m above datum where pristane/phytane
ratios of about 0.55 to 0.7 change to values of 0.85 to 1.0 (Fig. 5, Table 4).
This indicates a general shift in the redox regime, switching from
severely reducing conditions to still strongly reducing conditions at
about 7 m above the base of the L1 horizon. As discussed in the section
on redox conditions, a good correlation between the pristane/phytane
and phytane/n-C18 ratio is noted for the Pesciara site, which is
confirmed by elevated phytane/n-C18 ratios in the lower part of the
section (Fig. 5).
The change in environmental conditions is not reflected in the bulk
parameters, which show trends mostly affected by lithology or
texture. The HI values are enriched in samples 0201, 0202, 0207, and
0218, all of which are laminated micritic limestones. It is important to
note that laminitic sample 0218 is positioned in the upper section of
the Pesciara profile and according to its biomarker signature is notably
different from the underlying laminitic beds. This exemplifies that the
biomarker signal is not coupled to the bulk organic matter composi-
tion and is suitable to delineate more delicate changes in environ-
mental conditions.
The δ13C signature of the bulk organic matter also shows a vertical
trend of heavier δ13C values in the lower section and lighter δ13C
values in the upper section (Fig. 5), superimposed on this trend is a
tendency of heavier δ13C signatures for laminated micrites and lighter
δ13C values for the arenitic samples.
The differentiation between upper and lower section at the
Pesciara site is further reflected by the amount of terrigenous material
brought into the basin. The lower section shows a higher proportion of
land plant wax derived long-chain alkanes, whereas the upper section
is dominated by short-chain aquatic-derived n-alkanes (Fig. 5,
Table 4). This change in organic matter supply may be responsible
for the heavier δ13C values in the lower section. Influx of terrestrial
organic matter must be accompanied by a hydrodynamic regime that
allowed for transport of nutrients into the basin thus favoring higher
bioproductivity during deposition of sediments in the lower section. A
relationship between the autochthonous biomarker signals and the
allochthonous long-chain n-alkanes is thus established.
The biomarkers originating from aquatic organisms, i.e. algae or
cyanobacteria, reflect changes in environmental conditions by the
variability in short-chain n-alkane composition and the ratio of n-alkanes
versus isoprenoids and HBI. The algal community has changed at the
boundary between upper and lower section in that a notable predomi-
nance of n-C16 is established in the upper interval (Fig. 5). However, as
both n-C16 and n-C17 can be biosynthesized by various classes of algae
and cyanobacteria (Peters et al., 2005), a clear source allocation based on
exclusively these two compounds is not yet possible. Compound-specific
isotope analyses of both n-alkanes might provide a means of separating
cyanobacterial from algal input. The change in aquatic community
structure is also seen in the relative abundance of n-C17 versus the diatom
derived HBI20, the latter being dominant in the lower section (Fig. 5). The
shift in aquatic primary producers is reflected by several biomarker ratios
indicative of the primarily source controlled nature of the environmental
change at about 7 m above datum. The laminitic micrite of sample 0214
provides evidence that the changes across the profile are not simply
governed by lithofacies as this sample, despite its lithology being similar
to the lower section, shows a lower proportion of terrigenous long-chain
n-alkanes as well as diatom derived HBI.
A shift in the relative proportions of HBI with 25 versus 29 carbon
atoms may attest to either a change in the diatom community that
inhabited the Pesciara basin (Fig. 5) or may indicate a shift in preservation
conditions. As no organisms have been reported so far to biosynthesize
Fig. 6. 4Revised depositional model for the Pesciara Section, according to previous studies (Trevisani et al., 2005; Papazzoni and Trevisani, 2006) and data from this work. A) Depositional
setting during lowstand times, with effective threshold and permanent water stratification; these conditions are recorded in the lower part of the Pesciara Section. B) Depositional setting
during highstand times, with less effective threshold and temporary water stratification; these conditions are recorded in the upper part of the Pesciara Section.
C29 HBI (Rowland and Robson, 1990; Sinnighe Damsté et al., 2004; Peters
et al., 2005), the occurrence of the C29 HBI may be explained by
degradation of a C30 HBI. The coeval shifts in a variety of biomarker ratios
in a transition zone 7 m above datum (Fig. 5, Table 4) may thus reflect a
response to environmental change inducing establishment of a different
microbial association and/or a change in preservation conditions.
6. Conclusions
Investigation of kerogen and extractable lipid biomarker composi-
tion of 13 samples taken along a stratigraphic profile of the Eocene
Konservat-Lagerstätte of Pesciara di Bolca revealed new details on
organic matter input, its preservation conditions and factors influen-
cing the preservation of delicate fossil remains. These data allow to
confirm and refine the paleoenvironmental model presented by
Papazzoni and Trevisani (2006). Due to the small size and fragmenta-
tion of the outcrops in the Bolca area, a generalized depositional
model for the Pesciara is still affected by a speculative component.
Nevertheless, accumulating evidence continues to fit the model,
which is coherent both with the paleoecologic data from the literature
and with the geochemical and facies analyses.
The predominant origin of kerogenous organic matter in the
Pesciara sediments can be attributed to marine organisms with a
minor admixture of terrigenous material. Biomarkers reveal that the
terrigenic fraction is predominantly made up by land plant waxes that
were transported into the basin by eolian processes. The geochemical
data are in accordance with macrofossil remains of terrigenous plant
remains (Massalongo, 1859a,b), pollen, spores, and amber nodules
(Trevisani et al., 2005). A preferential enrichment of terrigenous
derived organic matter is noted for the only organic-rich (8.6% TOC)
sample from the basal fish-bearing L1 level, indicating the importance
of terrestrial freshwater run-off at this stage. Cyclic biomarkers show
evidence for angiosperm but not for gymnosperm derived lipids.
Molecular biomarkers indicate that the marine organic production
was dominated by diatoms. The lack of micropaleontological evidence
for diatom abundance may have arisen from dissolution of diatom tests
under alkaline pore water conditions; the dissolved biogenic silica could
be in turn the source of the observed silicified levels in different parts of
the Pesciara succession. Molecular biomarkers do not allow differentia-
tion between benthic and planktonic diatoms, thus a potential role of
benthic diatom mats in the preservation process of fossils cannot be
proven. It may be speculated that benthic diatoms in the Pesciara basin
may have fulfilled the role of substrate stabilization and fossil
preservation that in other settings has been ascribed to cyanobacterial
mats. The latter are assumed to have been of low abundance due to the
moderate amounts of mid-chain branched alkanes and other cyano-
bacterial biomarkers.
The environment of deposition in the Pesciara basin is inferred to have
been anoxic though not euxinic, with a water column stratification that
was due to episodic freshening of the upper water layers by monsoonal
rain and terrestrial run-off, as shown by terrigenous biomarkers and
fossils (Fig. 6). Stratification due to establishment of hypersaline bottom
waters as a consequence of highly evaporitic conditions on an equatorial
carbonate platform, as proposed for the Solnhofen type deposits, could
not be deduced from organic matter composition.
A marked shift in environmental conditions and community
structure was detected about 7 m above the datum, i.e. between
fossil-bearing levels L2 and L3. Diminished input of terrigenous organic
matter from this transition zone upwards was accompanied by less
reducing conditions. This indicates that water column stratification
and associated anoxia in the lower part of the Pesciara Section were
maintained by episodic establishment of a freshwater layer on top of
L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285 283
284 L. Schwark et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 272–285
unmixed oxygen depleted deep waters. The topography with a
circulation inhibiting submarine threshold favored stratification. The
decreasing input of terrestrial organic matter (mainly angiosperm
waxes) from 7 m upwards could be linked to a decrease in exposure of
emerged lands, due to a relative highstand developed after the
deposition of L2. In contrast, the lower part of the Pesciara succession
could represent a relative lowstand, with increased amount of lands
leading to greater amounts of angiosperm plants (source of the waxes
preserved in the basin).
This interpretation is confirmed by facies analysis, especially by
major thickness and continuity of L1 and L2 as compared with L3 and
L4. The relative sea-level lowstand maximized the effectiveness of the
threshold, inducing stagnation and very restricted circulation in the
deeper parts of the basin (Fig. 6A). On the contrary, during relative
sea-level highstand intervals the threshold was less effective, allowing
to some extent admixing and slight oxygenation of the bottom waters
with lower Eh values compared with the former (Fig. 6B).
Since the whole Pesciara succession has been dated to the upper
part of the SBZ 11 (Papazzoni and Trevisani, 2006), and the overall
duration of this biozone is 1.1–1.2 Ma (Serra-Kiel et al., 1998), we can
interpret the body of the Pesciara as a parasequence of the 4th order
(0.01–0.5 Ma).
In turn, this parasequence is subdivided into at least four higher-
order parasequences generated by minor sea-level fluctuations. Each
of these higher-order parasequences is represented by a couple of
laminated micrite with fish (lowstand deposits, LD) — biocalcarenites
with abundant benthic fossils (highstand deposits, HD). The trans-
gressive deposits (TD) are clearly represented at the top of L1 by an
undulated bed, 0 to 30-cm thick, of bioclastic limestone with silicified
extraclasts with alveolinas of the SBZ 10.
Acknowledgements
We thank Dr L. Langone (CNR-ISMAR Bologna), Dr D. Malferrari
(Modena University) and Dr M. Tonelli (CIGS; Modena University) for
technical support during this study. Prof. A. Rossi (Modena University)
provided X-ray analyses and helpful comments on the results.
Excellent analytical work by student technical assistants at Cologne
University is gratefully acknowledged.
This study was supported by funds from the Ministero dell'Uni-
versità e della Ricerca Scientifica (Resp. A. Ferretti), by Società
Paleontologica Italiana grant (Fondo per la Tutela del Patrimonio
Paleontologico), and by Museo Civico di Storia Naturale di Ferrara.
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Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Geochemical environment of the Coniacian–Santonian western tropical Atlantic at

Demerara Rise
C. März a,⁎, B. Beckmann b,1, C. Franke c, Christoph Vogt a, T. Wagner d, S. Kasten e
a
Department of Geosciences, University of Bremen, Klagenfurter Str., 28359 Bremen, Germany
b
Institute for Geology and Mineralogy, University of Cologne, Zülpicher Str. 49a, 50674 Cologne, Germany
c
Laboratoire des Sciences du Climat et de l'Environnement (LSCE), CEA-CNRS-UVSQ, 12 Avenue de la Terrasse, 91198 Gif-sur-Yvette, France
d
School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK
e
Alfred Wegener Institute for Polar and Marine Research, Am Handelshafen 12, 27570 Bremerhaven, Germany

A R T I C L E I N F O A B S T R A C T

Article history: Organic carbon-rich shales deposited during the Coniacian–Santonian Oceanic Anoxic Event 3 were drilled
Received 13 December 2007 during ODP Leg 207 at Demerara Rise. We present integrated high-resolution geochemical records of core
Received in revised form 13 May 2008 intervals from ODP Sites 1259 and 1261 both from nannofossil biozone CC14. Our results reveal systematic
Accepted 16 May 2008
variations in marine and detrital sediment contribution, depositional processes, and bottom water redox
conditions during black shale formation at two locations on Demerara Rise in different paleo-water depths. A
Keywords:
Oceanic anoxic event
combination of redox proxies (Fe/S, P/Al, C/P, redox-sensitive/sulfide-forming trace metals Mn, Cd, Mo, Ni, V,
Trace elements Zn) and other analytical approaches (bulk sediment composition, P speciation, electron microscopy, X-ray
Iron diffraction) evidence anoxic to sulfidic bottom water and sediment conditions throughout the deposition of
Phosphorus black shale. These extreme redox conditions persisted and were periodically punctuated by short-termed
Sediment source periods with less reducing bottom waters irrespective of paleo-water depth. Sediment supply at both sites
Redox changes was generally dominated by marine material (carbonate, organic matter, opal) although relationships of
Enrichment factors detrital proxies as well as glauconitic horizons support some influence of turbidites, winnowing bottom
currents and/or variable detritus sources, along with less reducing bottom water at the proposed shallower
location (ODP Site 1259). At Site 1261, located at greater paleo-depth, redox fluctuations were more regular,
and steady hemipelagic sedimentation sustained the development of mostly undisturbed lamination in the
sedimentary record. Strong similarities of the studied deposits exist with the stratigraphic older
Cenomanian–Turonian OAE2 black shale sections at Demerara Rise, suggesting that the primary mechanisms
controlling continental supply and ocean redox state were time-invariant and kept the western equatorial
Atlantic margin widely anoxic over millions of years.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Since Schlanger and Jenkyns (1976) introduced the original
concept of Oceanic Anoxic Events (OAEs), much progress has been
made in the understanding of the widespread deposition of organic
matter (OM)-rich sediments in the Cretaceous Proto-Atlantic and
adjacent seas. During ODP Leg 207, up to 90 m thick Cretaceous black
shale deposits, including OAE2 and OAE3 were recovered from
Demerara Rise (Erbacher et al., 2004; Mosher et al., 2007).
Cenomanian–Turonian OAE2 black shales from ODP Leg 207 have
been subject of intensive research (e.g. Erbacher et al., 2005; Friedrich
et al., 2006; Hardas and Mutterlose, 2006; Musavu-Moussavou and
⁎ Corresponding author. Present address: ICBM, University of Oldenburg, Carl-von-
Ossietzky-Str. 9-11, 26111 Oldenburg, Germany. Tel.: +49 441 798 3627.
E-mail address: cmaerz@icbm.de (C. März).
1
Present address: Federal Institute for Geosciences and Natural Resources, Stilleweg
2, 30655 Hannover, Germany.
Danelian, 2006; Forster et al., 2007a; Junium and Arthur, 2007;
Nederbragt et al., 2007) whereas far less is known about the
development of the later Coniacian–Santonian OAE3 in this critical
area of the tropical North Atlantic (Friedrich and Erbacher, 2006;
Beckmann et al., in press; März et al., in press). Given that OAE3
sediments from the adjacent tropical African margin (Deep Ivory
Basin, ODP Leg 159) revealed spectacular evidence of astronomically
forced sedimentary and redox cycles directly associated with African
climate variability (Wagner, 2002; Wagner et al., 2004; Beckmann
et al., 2005a,b; Flögel and Wagner, 2006) and the opening of the
Equatorial Atlantic (Wagner and Pletsch, 1999; Pletsch et al., 2001)
there is scope for more detailed investigation of this stratigraphic
interval at Demerara Rise. First geochemical studies revealed that
Demerara Rise black shales contain thermally immature marine OM
(Meyers et al., 2006; Forster et al., 2007b). Its slow degradation still
produces methane, which is anaerobically oxidized at the top of the
Cretaceous black shale succession via sulfate reduction, resulting in
sulfate depletion and long-lasting barite remobilization within the

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.05.004
 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301 287

black shale succession (Erbacher et al., 2004; Arndt et al., 2006). High
degrees of pyritization, but also sulfurized OM (Böttcher et al., 2006),
enrichments of Mo, V, Zn, and Mn depletion (Hetzel et al., 2006)
indicate overall oxygen-depleted, periodically even sulfidic bottom
waters. Enrichments of P as well as high amounts of Ba (despite
diagenetic redistribution) support enhanced nutrient supply and high
productivity during black shale deposition (Arndt et al., 2006; Hetzel
et al., 2006). We recently explored a broad variety of redox proxies in
OAE3 black shales at ODP Site 1261. The records are consistent and
show cyclic and rapid redox fluctuations from sulfidic to anoxic, non-
sulfidic conditions in bottom waters (März et al., in press) obviously
triggered astronomically by short eccentricity cycles (Flögel et al., in
press).
In this study we add evidence to the findings of the Cretaceous low
latitude Atlantic by applying a wide analytical spectrum in high
temporal resolution to ODP Sites 1259 and 1261 from Demerara Rise.
The main goal is to trace changes in deep ocean redox state, sediment
sources and depositional processes along a bathymetric transect
across the S-American continental margin. To achieve these goals we
selected nannofossil biozone CC14 intervals from both sites and
applied major and trace element geochemistry, P speciation, X-ray
diffraction, and scanning electron microscopy. For completeness,
some of the results presented by März et al. (in press) are shown
here, however, we emphasize that this study takes the discussion
forward by comparing synchronous stratigraphic intervals from two
different paleo-water depths, and by adding new geochemical
information on sediment sources and depositional processes. To
place the results from OAE3 into wider perspective we compare them
with new geochemical data from OAE2 at Demerara Rise (Brumsack,
2006; Junium and Arthur, 2007; Hetzel et al., 2009).
2. Material and methods
The ODP Leg 207 Sites 1259 and 1261 were drilled on Demerara
Rise, in water depths of 2354 m and 1899 m on the northern and
northwestern slope, respectively (Fig. 1; Erbacher et al., 2004). For this
high-resolution study, we chose core intervals from Sites 1259
(499.60–500.61 meters composite depth, mcd, 101 cm) and 1261
(570.20–571.40 mcd, 120 cm) and sampled them in continuous 1 cm
resolution. For comparison we selected intervals from the same
stratigraphic nannofossil biozone CC14 (Coniacian–Santonian), using
the nannofossil stratigraphy published by Erbacher et al. (2004) that
was recently refined by Flögel et al. (in press) for Site 1261 and by
Bornemann et al. (2008) for Site 1259. Sedimentation rates were
~5.4 mm/ka at Site 1261 (Flögel et al., in press), and ~2–3 mm/ka at
Site 1259 (Bornemann et al., 2008). Thus, both sampled intervals are

Fig. 1. a) Global plate-tectonic reconstruction for 80 Ma BP (after Hay et al., 1999; Wagner et al., 2004). Grey areas represent regions above sea level, white areas represent oceans,
black lines depict plate boundaries. Black dots indicate locations of reported Late Cretaceous organic matter-rich deposits (Wagner et al., 2004 and references therein). b) Close-up of
the equatorial Proto-Atlantic, with Demerara Rise marked by the black rectangle. c) Present-day bathymetry of Demerara Rise, with drill sites 1257–1261.
288 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301
condensed successions, with sedimentation rates at Site 1261 about
twice as high as at Site 1259. Being aware of these differences, our
geochemical comparison does not aim at layer-to-layer correlation —
although both intervals were deposited during nannofossil biozone
CC14, there might still be a temporal offset. We rather compare both
sites in terms of general sedimentation patterns and geochemical
characteristics of sediments and bottom waters.
Sample splits taken at the ODP Core Repository Bremen were frozen,
freeze-dried and ground in an agate mortar. Total organic carbon (TOC)
and carbonate contents were determined with a Leco CS 200. First, total
carbon (TC) was measured, then a sample aliquot was decalcified with
12.5% HCl, washed twice and dried at 60 °C to determine TOC. The CaCO3
content (%) was calculated as (TC − TOC) ⁎ 8.33. Calcite was the only
carbonate mineral detected by X-ray diffraction (XRD), other carbonates
(e.g. dolomite, rhodochrosite) are not of quantitative importance
(b1 wt.%). Minor amounts might be present especially at Site 1259,
but for simplicity are summarized as CaCO3. Several standards with C
contents between 0.5 and 12% were applied to keep the accuracy of the
measurement at N97%.
About 50 mg of each sample were subjected to a microwave total
acid digestion procedure (3 ml HNO3, 2 ml HCl and 2 ml HF; heated up
to ~ 210 °C in closed pressure-tight teflon containers; acids were fumed
off with a special vacuum device, dry samples were redissolved with
HNO3). Major and minor elements were measured with an Inductively
Coupled Plasma Optical Emission Spectrometer (ICP-OES, Perkin Elmer
3300RL) in triplicate to assure a standard deviation of b5%. Accuracy of
the digestion and measurements was assured by running blanks and
the USGS standard MAG-1 and in-house standards MAX-1 and CAMAX
with the sample sets. Elemental concentrations were within the 5%
range of certified values for the standard materials, respective standard
deviations of triplicate measurements were b3% for major and b5% for
trace elements. For details, we refer to Schulz (2004) and www.
geochemie.uni-bremen.de/koelling/MGCmain.html. Bulk elemental
contents and TOC were normalized to Al to compensate for variable
dilution of the geochemical record by biogenic and diagenetic
components. Element contents calculated on carbonate-free basis
(CFB; data not shown), an alternative method to compensate for
variable biogenic calcite dilution, showed very similar patterns.
A sequential phosphate extraction (SEDEX method by Ruttenberg,
1992; modified after Schenau and De Lange, 2000; Schenau et al.,
2000) was applied to selected P-rich samples (500.13–500.53 mcd at
Site 1259 and 570.5–570.64 mcd at Site 1261), resulting in differentia-
tion between various phosphorus-bearing phases in the sediment
(Table 1). Extracted P was analysed photometrically (Steps I, III–V) or
via ICP-AES (Step II).
Table 1
Different steps of the applied sequential phosphate extraction, the respective extraction
solutions and extracted fractions of phosphate
Step Reagents P component extracted
I 25 ml 2 M NH4Cl (pH 7, shake for 4 h), Pvar: pore water phosphate, amorphous
repetition up to 20× Ca-rich apatite precursor mineral,
phosphate loosely sorbed to carbonates
and clay minerals, fish bones
(= biogenic hydroxyapatite)
II 25 ml Na-dithionite solution, citrate- Piron: phosphate bound to iron
buffered (pH 7.5, shake for 8 h); wash (oxyhydr)oxides, including secondarily
with 25 ml 2 M NH4Cl (shake for 2 h); oxidized Fe(II)-phophates as vivianite
wash with 25 ml dem. water (shake for
2 h)
III 25 ml 1 M Na-acetate solution (pH 4, Pauth: authigenic apatite (CFA,
for 6 h); wash with 25 ml 2 M NH4Cl francolite)
(shake for 2 h); wash with 25 ml dem.
water (shake for 2 h)
IV 25 ml 1 M HCl (shake for 24 h); wash Pdet: detrital apatite
with 25 ml dem. water (shake for 2 h)
after ignition at 550 °C
V 25 ml 1 M HCl (shake for 24 h) Porg: phosphate bound to organic
matter
X-ray diffraction (XRD) was used to reveal the general mineralogy
of the core sections, and to support P extraction data by detecting the
apatite fraction of the bulk P pool. X-ray diffractograms of freeze-dried,
ground samples were produced with a Philips X'Pert Pro multipurpose
diffractometer equipped with a Cu-tube (k" 1.541, 45 kV, 40 mA), a
fixed divergence slit of 1/4°, a 16 samples changer, a secondary
monochromator and the X'Celerator detector system. Samples were
scanned continuously from 3–85° 2θ, with a calculated step size of
0.016° 2θ (calculated time per step 100 s). Mineral identification and
semi-quantification was done with the Philips software X'Pert High-
Score™ (as Relative Intensity Ratio values, calculated as ratio of the
most intense reflex of a specific mineral phase to most intense reflex of
pure corundum; Chung, 1974; Vogt et al., 2002).
Heavy liquid separation (Franke et al., 2007) was applied to
selected samples, extracting the mineral fraction with a density
of N3.0 g/cm3 (e.g. barite, pyrite, calcium-fluorapatite = CFA). We used
~0.5–1 g of freeze-dried, homogenized sediment and a Na-polytung-
state solution (3.0 g/cm3; ~25 ml per sample). Sediment solutions
were shaken manually and dispersed in an ultrasonic bath. Suspen-
sions were centrifuged (20 min, 4000 rps), and the heavy liquid mirror
and supernatant fraction (b3.0 g/cm3) were removed with a pipette.
The remaining heavy fraction was vacuum-filtered (0.2 µm), and
washed several times with bi-distilled water. Filtered extracts were
dispersed in bi-distilled water and centrifuged several times to
prevent Na-polytungstate contamination. Dried extracts were pre-
pared for Scanning Electron Microscopy (SEM, Philips XL30 SFEG,
12 kV acceleration voltage). Unconsolidated grains were dispersed
onto a carbon sticker on a standard Al stub, and covered with a few nm
thick carbon layer to prevent surface charging during SEM analysis.
Secondary electron (SE) and backscattered electron (BSE) detectors
were used for imaging. For elemental composition, energy-dispersive
X-ray spectroscopy (EDS; e.g. Goldstein et al., 1992) was applied and
semi-quantification was achieved using the EDAX PhiRhoZ software.
3. Results
3.1. Lithology
OAE3 sediments at Site 1261 consist of finely laminated black
claystone and nannofossil claystone (Erbacher et al., 2004). Visual
inspection of the Site 1261 core section revealed black intervals of few
centimeters thickness containing light, roundish components of up to
a few mm in diameter. The components are elongate, lense-shaped,
and embedded into the stratification and bear no signs of physical
disturbance throughout the entire study interval. Similarly, at Site
1259 the studied core interval displays lamination in the upper
~ 70 cm of the interval (499.60–500.30 mcd), as well as cyclic
occurrence of layers with round to elliptic, whitish components of
up to a few mm in size. However, in the lower part a glauconitic
horizon (Erbacher et al., 2004; here referred to as GH) is visible as a
sandy, light horizon of ~ 20 cm thickness, comprising a relatively
unsorted framework of white, mm- to cm-sized grains. Under the light
microscope, glauconite grains from the GH appear as green to blue-
green crystals, fragments or as green-whitish aggregates.
3.2. Total organic carbon and carbonate
The TOC content at Site 1261 is generally higher compared to Site
1259 (average of 7.7 wt.% versus 6.1 wt.%, respectively; Fig. 2a), as is
the TOC/Al ratio (average of 3.6 versus 2.8; Fig. 2b) and TOC (CFB)
(average of 18.7 wt.% versus 15.8 wt.%; data not shown. The amplitude
between TOC maxima and minima is on the order of 7 wt.% at both
sites, with values of 4.4–11.7 wt.% at Site 1261 and 2.9–10.2 wt.% at Site
1259 (Fig. 2a), without clear repetitive patterns. Different from that,
the TOC/Al records show regular cyclic patterns at both sites, with the
exception of much lower TOC/Al ratios in the lower part of the 1259
 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301 289

Fig. 2. Chemical composition of ODP Sites 1261, 570.2–571.4 (meters composite depth, mcd), and 1259, 499.6–500.7 mcd. (a) Total organic carbon (TOC, wt.%), (b) TOC/Al (%/%),
(c) carbonate (wt.%), (d) Al (g/kg) versus core depth. The grey-shaded areas indicate low carbonate contents, the glauconitic horizon (GH) is marked by the dotted area.

section (below 500.30 mcd; Fig. 2b). The carbonate record at Site 1261
displays background values of ~50–70 wt.%, interrupted by four
intervals of 5–10 cm thickness, each with carbonate contents of only
20–30 wt.% (Fig. 2c), coincident with lowest TOC/Al values. In contrast,
the carbonate content at Site 1259 does not show the same systematic
variations, but varies in a more irregular manner between 30–70 wt.%
(Fig. 2c). Only in the lowest part of the interval (below 500.48 mcd),
carbonate contents reach 70–100 wt.%.
3.3. Detrital elements (Al, K, Mg, Ti, Zr)
Aluminum is mainly incorporated into detrital silicates in
continental margin settings like Demerara Rise and thus represents
continental input. Other typically detrital elements are K, Mg, Ti and Zr
(Fig. 3). At Site 1261, background Al values of 15–25 g/kg are
interrupted by sharp peaks of 35–40 g/kg (Fig. 2d). Calculation on
CFB, however, removes these peaks, and documents minor fluctua-
tions in Al (CFB; max. value 63.7 g/kg, min. value 45.4 g/kg, mean value
52.8 g/kg; data not shown). A clear anti-correlation of Al with
carbonate (R2 = 0.91; correlation coefficients always given as linear
correlations; Figs. 2d, 4a) documents mutual dilution of detrital and
biogenic material. At Site 1259, Al contents are within a similar range
(10–35 g/kg; Fig. 2d), but the Al-carbonate relationship is weaker
(R2 = 0.59; Fig. 4a). Terrigenous elements bound to the heavy mineral
fraction include Ti and Zr (Fig. 3a, b). At Site 1261, correlation
coefficients are R2 = 0.99 for Al with Ti, and R2 = 0.93 with Zr (Fig. 4b, c).
At Site 1259, the correlation of Al with Ti is strong (R2 = 0.98), but the
one of Al with Zr is weaker (Fig. 4b, c; R2 = 0.63). Typical elements of
light silicates are K and Mg (Fig. 3c, d), but they are also present in sea
water, and Mg may be incorporated in carbonates (although no
dolomite was detected via XRD). Comparable to Ti and Zr, relation-
ships of Al with K and Mg at Site 1261 are strong (R2 = 0.98 for Al with
K, 0.94 for Al with Mg; Fig. 4d, e). At Site 1259, correlations of Al with K
and Mg are overall weaker, with R2 = 0.65 for Al with K, and R2 = 0.36
for Al with Mg (Fig. 4d, e).
3.4. Redox-sensitive trace elements (Cd, Mn, Mo, Ni, V, Zn)
The investigated trace elements participate strongly in redox
reactions and may become authigenically enriched or depleted in
sediments deposited under oxygen-free conditions, making them
frequently applied tracers of paleoredox conditions (e.g. François,
1988; Calvert and Pedersen, 1993; Dean et al., 1997; Morford and
Emerson, 1999; recent reviews by Brumsack, 2006; Tribovillard et al.,
2006). The degree of enrichment/depletion is calculated as enrich-
ment factor (EF) relative to a standard material (average shale = AS;
Turekian and Wedepohl, 1961):
EFelement ¼ ðelement=AlÞsample =ðelement=AlÞaverage shale
The use of AS as reference material may get stressed by non-uniform
lithologies in the detrital source area (Van der Weijden, 2002), but this
290 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301

Fig. 3. Chemical composition of ODP Sites 1261, 570.2–571.4 mcd, and 1259, 499.6–500.7 mcd. (a) Ti/Al, (b) Zr/Al (both as ppm/%), (c) K/Al, (d) Mg/Al (both as %/%) versus core depth
(meters composite depth, mcd). The grey-shaded areas indicate less reducing conditions, the glauconitic horizon (GH) is marked by the dotted area.

potential bias is uncritical for the presented trace metals, with low
contents in AS and/or strong incorporation into biological or
authigenic processes (Brumsack, 2006). In the studied core sections
we identified two categories of redox-sensitive trace elements.
3.4.1. Manganese
Values of Mn/Al are ~ 20–45 ppm/% across the Site 1261 and the
upper Site 1259 interval (above 500.10 mcd). Values of ~ 60–90 ppm/%
are reached in the lowest part of the 1259 section (below 500.48 mcd;
Fig. 5a). The Mn/Al record displays a rather strong correlation with
carbonate (Figs. 5a, 6a). At Site 1261, correlation coefficients are
similar for carbonate-poorer (R2 = 0.78, n = 19) and carbonate-richer
(R2 = 0.79, n = 96) samples if the carbonate content threshold is set to
55 wt.%. Respective correlations both follow positive trends, but with
different slopes. At Site 1259, the Mn/Al to carbonate correlation is
only high for carbonate-richer samples (R2 = 0.74, n = 35; Fig. 6b).
Average EFs for Mn at Sites 1259 and 1261 are ~ 0.36 (up to 1.0) and
~ 0.30 (up to 0.49), respectively, indicating Mn depletion throughout
the investigated sediment intervals (Table 2; Fig. 7).
Maximum values of Cd/Al, V/Al and Zn/Al ratios are similar at both
sites, but Mo/Al and Ni/Al maxima are much lower at Site 1259 (Fig. 5).
As further differences between trace element/Al profiles at Site 1261,
all trace element/Al ratios are lowest within the carbonate-poor layers
(grey bars), but the positions of the maxima vary. While Cd/Al, V/Al
and Zn/Al are highest right above the carbonate-poor layers and
gradually decrease upsection, Mo/Al and Ni/Al continuously increase
upcore and reach maximum values right below the next carbonate-
poor layer. Thus, Mo/Al and Ni/Al exhibit rather strong correlations
with the TOC/Al and S/Al records (R2 = 0.73 to 0.89; Fig. 6c–f), while
there are no significant correlations of Cd/Al, V/Al and Zn/Al with TOC/
Al and S/Al (R2 b 0.01). Site 1259 exhibits the same general trace
element/Al patterns, although trace element/Al minima (grey bars) do
not match as precisely with carbonate minima as at Site 1261. Average
trace element EFs are within the same range at both sites (Table 2;
Fig. 7). Notably, even lowest trace element/Al ratios are still (strongly)
enriched relative to AS (Fig. 5b–f; AS values indicated by black arrows
on the X-axis). The GH is characterised by consistently lower trace
element/Al ratios (Fig. 5b–f).

3.4.2. Cadmium, molybdenum, nickel, vanadium, zinc
Throughout the study interval at Site 1261 and the upper part at
Site 1259 (499.60–500.10 mcd) there are cyclic patterns of Cd/Al, Mo/
Al, Ni/Al, V/Al and Zn/Al (Fig. 5b–f). The cycles are better resolved at
Site 1261 compared to Site 1259, partly because the latter had a lower
sedimentation rate during biozone CC14 (Bornemann et al., 2008).
3.5. Iron and sulfur
The Fe/Al ratios of the samples investigated are within a relatively
narrow range at Site 1261 (~ 0.44–0.57), while this range is much
wider at Site 1259 (~ 0.41–1.68), highest Fe/Al ratios being reached
within the glauconite horizon (Fig. 8a). Small enrichments of Fe/Al at
 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301
Fig. 4. Cross plots of: (a) CaCO3 to Al, (b) Ti to Al, (c) Zr to Al, (d) K to Al, (e) Mg to Al, (f) S/Al to TOC/Al for Sites 1259 (dots) and 1261 (crosses), with respective linear correlation
coefficients (R2).
Site 1261 are located directly below the carbonate-poor intervals (grey
bars). However, there are no such peaks in the Fe (CFB) plot (not
shown here). At Site 1259, there are two Fe/Al peaks in the central part
of the interval, but these values are more than doubled in the
glauconite horizon. The EF of Fe at Site 1261 is ~0.9 on average, with
maxima of ~1.1 (Table 2). At Site 1259, a slightly higher EF of ~ 1.3 is
observed, but Fe/Al ratios that are consistently N1.0 are mostly
confined to the GH (maximum values = 3.1; AS value = 0.54; Table 2).
The Fe/S ratios (Fig. 8d) can be used as indicator for the amount of
sulfide-bound Fe — the lower the ratio, the more Fe is sulfide-bound.
The Fe/S ratio at Site 1261 ranges between 0.4 and 0.9, and highest
values are reached within the carbonate-poor intervals, from where
they gradually decrease upcore (Fig. 8d). Thus, highest Fe/S values
coincide with lowest trace metal/Al and TOC/Al values. In the upper
part of Site 1259 (499.60–500.10 mcd), Fe/S correlates with the same
parameters as at Site 1261, but Fe/S values are markedly higher (~ 0.6–
1.4), and within the GH, Fe/S reaches maximum values of 2.2 (Fig. 8d).
Notably, S/Al ratios (Fig. 8e) correlate strongly with TOC/Al at Site 1261
(R2 = 0.83; Fig. 4f), while the respective correlation is much weaker at
Site 1259 (R2 = 0.27; Fig. 4f).
3.6. Phosphorus
At Site 1261, consistently low P contents of b0.1 wt.% (75 of 115
samples in total) and P/Al ratios of b0.1 are found (Fig. 8b). However,
pronounced peaks with P contents of up to 2.5 wt.% and high P/Al
ratios (up to ~ 0.8) cyclically occur within the carbonate-poor layers. At
Site 1259, we observe P-poor (b0.1 wt.%; 22 out of 101 samples) and P-
rich layers as well, but their pattern is less regular, P peaks are not as
distinct, and P/Al ratios are generally higher than at Site 1261 (Fig. 8b).
Especially the GH at Site 1259 (499.60–500.10 mcd) is characterized
by P contents of N2.0 wt.% (up to 5.2 wt.%), and P/Al ratios of N1.0 (up
to 3.3), with higher values at the base of the GH. The TOC to bulk P
ratios (C/P), which is ~ 106:1 in average marine biomass (Redfield,
1958), are variable at both studied sites. C/P ratios range from 3.0 to
301 at Site 1261, and from 0.57 to 372 at Site 1259 (Fig. 8c). Generally,
291
highest C/P values coincide with high values of TOC/Al and S/Al, and
lowest C/P values with P/Al peaks.
The sequential phosphate extraction yields information about P
speciation (Fig. 9a, b). Note that P extractions in both cores were
confined to small stratigraphic intervals. The interval at Site 1261 was
chosen as all four P peaks, like all the other elemental records, are
repetitive and of similar magnitude (Fig. 8), and most probably
document similar geochemical processes and conditions. The upper P
peak at Site 1259 was chosen for the same reason (Fig. 8b), while the
glauconite horizon was selected due to its markedly different
geochemistry.
The investigated P peak at Site 1261 (8 samples; Fig. 9a) and the
upper studied P peak at Site 1259 (7 samples, without GH; Fig. 9b)
have a similar P speciation: Fish bones (Step I) and OM-bound P
(Step V) make up a minor fraction of the bulk P pool (b10%) at both
sites. Detrital apatite (Step IV) is more significant at Site 1259 (~ 0–26%,
average of ~ 9%) than at Site 1261 (~ 0.2–9%, average of ~ 5%).
Authigenic apatite (Step III) is clearly the dominant fraction at Site
1259 (~ 17–87%, average of ~ 60%), and is also of major importance at
Site 1261 (~ 16–81%, average of ~43%). Iron-bound P (Step II) is the
dominant fraction at Site 1261 (~ 23–66%, average of ~ 49%), while its
contribution to the P pool is substantially smaller at Site 1259 (~4–
27%, average of ~ 17%). Within the GH at Site 1259 (6 samples; Fig. 9b),
the fish bone and OM-bound P fractions are likewise rather
unimportant (b7%). The sum of iron-bound P and authigenic apatite
(~ 6–35% with ~ 21% on average, and ~36–88% ~with 58% on average,
respectively) constitutes the majority of the P pool. In relation to the
other P peaks, detrital apatite is more significant within the GH (~1–
42%, average of ~ 22%).
3.7. SEM and XRD results
The majority of particles of the density fraction N3.0 g/cm3 were
calcium-fluorapatite (CFA), Fe sulfides (mostly pyrite), Zn sulfides and
barite. The analysed samples were selected from core intervals
representative for the different geochemical and depositional
292 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301

Fig. 5. Chemical composition of ODP Sites 1261, 570.2–571.4 mcd, and 1259, 499.6–500.7 mcd. (a) Mn/Al, (b) Cd/Al, (c) Mo/Al, (d) Ni/Al, (e) V/Al, (f) Zn/Al (all as ppm/%) versus core
depth (mcd). Arrows at X-axis indicate respective element/Al values of average shale (Turekian and Wedepohl, 1961).

conditions, and are considered as representative in terms of
composition, size and morphology of the dominant heavy minerals.
Pyrite and other Fe sulfides are frequent in all samples, and occur
as euhedral or cubic crystals or as framboids of ~ 2–20 µm in diameter
(Fig. 10a). The atomic Fe:S ratios of the Fe sulfides are 0.5–1.0
according to the applied quantification software, indicating the
presence of greigite and mackinawite next to pyrite. Zinc sulfides
were observed in the Zn-rich samples (Site 1259, 499.82 and
499.88 mcd) as idiomorphic stochiometric ZnS crystals of 1–5 µm
diameter. Crystals were found either dispersed or in framboid-like
aggregates of ~ 15 µm diameter (Fig. 10b). Barite is present in most of
the samples, but rather dispersed, and was observed in the grain size
 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301 293

Fig. 6. Cross plots of: CaCO3 to Mn/Al for Sites 1261 (a) and 1259 (b), respectively of carbonate-poorer (dots) and -richer (crosses) samples; (c) Mo/Al to TOC/Al, (d) Ni/Al to TOC/Al, (e)
Mo/Al to S/Al, (f) Ni/Al to TOC/Al for Sites 1259 (dots) and 1261 (crosses), with respective linear correlation coefficients (R2).

range of 2–30 µm. Most barites appear as uneven, angular, massive
grains with signs of fractures (Fig. 10c), most likely fragments of larger
grains that were broken into smaller pieces during sediment grinding.
Apatite grains represent the dominant heavy mineral in the P-rich
samples, while they are absent in the P-poor ones. They cover a wide
range of grain sizes, from few µm to several 100 µm in diameter.
Irregular aggregates of smaller crystals are most likely of authigenic
origin (Fig. 10d). However, most apatite particles have a massive,
compact morphology and partly medium to strong rounding, probably
due to transportation (Fig. 10d).
In support of the sequential P extraction, large amounts of CFA
were detected via structural analysis with X-ray diffraction. Other
common minerals apart from CFA encountered in all analysed samples
Table 2
Maximum and mean elemental enrichment factors (EFs) for the investigated intervals
from ODP Sites 1261 and 1259, Demerara Rise, compared to EFs of Cenomanian–
Turonian Boundary Event (CTBE) black shales from Demerara Rise (1) and various CTBE
location worldwide (2; Brumsack, 2006)
via X-ray diffraction were calcite (confirming the geochemical
analysis) and clinoptilolite ((Na,K,Ca)2–3Al3(Al,Si)2Si13O36·12(H2O)).
4. Discussion
4.1. Terrigenous versus marine sediment input
Input of Al, K, Mg, Ti and Zr at Sites 1259 and 1261 was rather low,
with e.g. Al constituting only ~ 1–4 wt.% of bulk sediment. Persistent
lamination and strong correlation of Al with K, Mg, Ti and Zr (R2 N 0.9)
at Site 1261 support steady sedimentation without bioturbation or
mass wasting, and probably one single detrital source area. Deposi-
tional conditions were different at Site 1259 as indicated by the
element/Al plots (Fig. 3) and weaker relationships between the
detrital proxy elements (Fig. 4). They support repeated interruptions
of sedimentation by mass wasting or winnowing of light particles
(Nederbragt et al., 2007) and/or change of the detrital source area at

Mean EF of Max. EF of Mean EF of Max. EF of EF of (1) EF of (2)

1261 vs. AS 1261 vs. AS 1259 vs. AS 1259 vs. AS vs. AS vs. AS
Ba/Al 4.78 5.85 3.04 6.39 2.35 3.10
Cd/Al 212 763 298 1004 170 184
Fe/Al 0.88 1.03 1.28 3.14 1.16 1.44
K/Al 0.96 1.03 1.06 1.85 0.86 0.93
Mg/Al 1.12 1.37 1.35 2.49 1.41 1.29
Mn/Al 0.30 0.49 0.36 1.10 0.44 1.29
Mo/Al 130 207 74.2 164 127 208
Ni/Al 10.4 16.1 8.74 13.7 10.6 11.5
P/Al 13.5 71.8 67.2 418 8.80 5.91
S/Al 30.9 38.8 27.5 46.5 – –
Ti/Al 0.83 0.85 0.84 0.85 1.01 0.96
V/Al 30.7 46.8 32.7 46.8 33.2 18.4
Fig. 7. Bar plots displaying mean elemental enrichment factors (EFs; note logarithmic
Zn/Al 30.9 86.7 35.1 86.7 22.8 42.5
scale) of Sites 1259 and 1261, as well as of OAE2 black shale from Demerara Rise
Zr/Al 0.67 0.80 0.70 0.80 0.83 0.99
(Brumsack, 2006) and OAE2 mean (from various OAE2 locations by Brumsack, 2006),
All EFs shown are calculated from element/Al ratios relative to average shale (AS; relative to average shale (Turekian and Wedepohl, 1961). Dashed lines indicate EFs of 5,
Turekian and Wedepohl, 1961). 30 and 100.
294 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301

Fig. 8. Chemical composition of ODP Sites 1261, 570.2–571.4 mcd, and 1259, 499.6–500.7 mcd. (a) Fe/Al, (b) P/Al, (c) C/P, (d) Fe/S, (e) S/Al (all as %/%) versus core depth (mcd). Boxes in
(b) mark the intervals of sequential P extraction. The dashed lines (c) indicate the C/P ratio of average marine organic plankton (after Redfield, 1958).

Site 1259. A possible explanation for the small amount of continental
material reaching the relatively proximal Sites 1259 and 1261 (Fig. 1c)
could be the trapping of most detrital matter on the flooded shelf area
due to high sea level (Mosher et al., 2007; Nederbragt et al., 2007) in
the upper Cretaceous.
The observed cyclicity of the Al record, particularly at Site 1261, is
attributed to variable dilution of the detrital signal by CaCO3 which
constitutes ~30–70 wt.% of bulk sediment at both sites, supporting a
strong influence of carbonate productivity on sedimentation. X-ray
diffraction data from both sites reveal the presence of large amounts
of clinoptilolite. Clinoptilolite is one of the most common zeolite
minerals in marine pelagic sediments, and has previously been
described in Cretaceous black shales from the North Atlantic (Thurow,
1988). It is formed authigenically by dissolution of amorphous SiO2
 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301
Fig. 9. Cummulative extracted P fractions at (a) Site 1261 (570.56–570.64 mcd) and (b) Site 1259 (500.1–500.53 mcd) in g PO4/kg sediment versus core depth (mcd). Explanation of
extraction steps in Table 1. Note that compared to other geochemical data presented, P extraction was only applied to comparably small core intervals.
(volcanic glass, opal tests as Si source) during burial diagenesis (e.g.
Kastner, 1980). In Demerara Rise black shales, preservation of siliceous
radiolarian tests is generally poor (Erbacher et al., 2004; Musavu-
Moussavou and Danelian, 2006; Nederbragt et al., 2007), most
probably related to extensive silica diagenesis in these deeply buried
sediments (e.g. Kastner, 1980; Thurow, 1988). Karpoff et al. (2007)
regarded clinoptilolite as a diagnostic proxy for paleoproductivity in a
Miocene marine setting. We therefore assume that clinoptilolite in the
studied samples is derived from dissolution-reprecipitation reactions
of biogenic silica, and thus indicative of opal productivity at the
Coniacian–Santonian Demerara Rise. In further support for elevated
marine primary paleoproductivity, organic geochemical studies
within Cretaceous black shales at Demerara Rise (e.g. Meyers et al.,
2006; Forster et al., 2007b; Beckmann et al., in press) proved an overall
high contribution of fresh marine OM to the bulk sediment.
Taking all these results into account we infer a depositional regime
at both ODP Sites that was dominated by strong biogenic marine input.
This conclusion is consistent with interpretations for OAE3 black shales
from the Deep Ivory Basin (ODP Site 959) and OAE2 black shale from
the Tarfaya shelf basin off SW Morocco (e.g. Wagner, 2002; Wagner
et al., 2004; Beckmann et al., 2005a,b). Estimates of paleoproductivity
based on the barite record are hampered by diagenesis (Brumsack,
2006). Pore water profiles of SO42− and Ba2+ (Erbacher et al., 2004)
indicate sulfate depletion throughout the black shales at Demerara
Rise, resulting in barite dissolution in this interval for the last ~ 86 Ma
(Arndt et al., 2006). Despite overall Ba enrichment relative to AS
(Fig. 7), SEM analyses of samples from ODP Sites 1259 and 1261 did not
identify any biogenic barite crystals, which are generally smaller than
diagenetic ones (0.5–5 µm versus 20–700 µm), and form elliptical or
euhedral crystals or aggregates (Torres et al., 1996; Paytan et al., 2004;
Paytan and Griffith, 2007). Instead, we detected numerous (fragments
of) most probably diagenetic barite particles (Fig. 10c).
4.2. Redox-sensitive elements
Combining records of different redox-sensitive (trace) elements is
a well established approach for reconstructing past redox conditions.
295
The interpretation of redox-sensitive (trace) metals investigated at
Demerara Rise will be preceded by a short introduction into its
behaviour under variable redox conditions.
4.2.1. Manganese
In general, Mn is reductively leached from marine sediments under
sub- to anoxic conditions (e.g. Froelich et al., 1979; Klinkhammer and
Bender, 1980; Lewis and Landing, 1991; Burdige, 1993; Morford and
Emerson, 1999). In a stratified anoxic water body, Mn2+/Mn (oxyhydr)
oxide cycling can occur shortly above the oxic/anoxic transition (e.g.
Black Sea, Cariaco Basin; Tebo, 1991; Yakushev et al., 2007; Percy et al.,
in press), and may thus scavenge and shuttle other trace metals to the
deeper, anoxic water column (e.g. Morford et al., 2005; Brumsack,
2006; Tribovillard et al., 2006). In an open margin oxygen minimum
zone (OMZ), Mn2+ leached from the underlying sediment may partly
diffuse out of the OMZ (e.g. Klinkhammer and Bender, 1980; Lewis and
Luther, 2000; Brumsack, 2006), resulting in sedimentary Mn deple-
tion. The significant Mn depletion within the studied OAE3 intervals
(except for the lowest part of the 1259 interval) indicates sedimentary
Mn leaching under constantly sub-/anoxic conditions (Fig. 5a).
However, the low amounts of sedimentary Mn appear to be bound
to carbonate as indicated by a strong correlation between carbonate
and Mn/Al at least for carbonate-rich samples (Fig. 6a, b). By XRD
analyses, no Mn carbonate was detected, probably due to its low
contents (b1 wt.%). The Mn to carbonate coupling is most obvious in
the bottom part of the 1259 section (below 500.48 mcd; Fig. 4a), where
both Mn/Al and carbonate reach maximum values, implying sub-
stantial Mn carbonate (rhodochrosite) formation. Minor differences in
the degree of depletion at both sites may be due to higher
sedimentation rates at Site 1261 (resulting in higher time resolution
of the sample set). Alternatively, physical sedimentation processes at
Site 1259 might have disturbed the carbonate–Mn correlation. The
reason for different slopes of Mn and carbonate correlation (Fig. 6a, b)
could be due to variations in the contribution of rhodochrosite to bulk
carbonate. More precisely, the best fit correlation line for carbonate-
richer samples at Site 1261 has a positive intercept with the carbonate
axis (Fig. 6a), indicating that other carbonate phases are present in
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these samples. The respective line for carbonate-poorer samples
intercepts with the Mn/Al axis, indicating that Mn is not only bound in
carbonates, but probably also to silicates or even oxides. The formation
of Mn carbonates is most probably a diagenetic process close to the
sediment surface, where OM degradation via Mn (oxyhydr)oxide
reduction increases pore water alkalinity and Mn2+ (e.g. Baltic Sea;
Huckriede and Meischner, 1996; Neumann et al., 2002). However,
carbonate–Mn correlation might also be obtained syngenetically by
Mn–carbonate overgrowths on carbonate tests within Mn2+-enriched
anoxic water bodies (Brumsack, 2006), which could have been the case
during biozone CC14 at Sites 1259 and 1261. Still, relatively elevated
Mn/Al and carbonate contents at the bottom of 1259 might indicate
intermittent and minor influence of oxygen and diagenetic rhodo-
chrosite precipitation. Precipitation of Mn sulfides is generally
neglected as Mn sink in black shales, as is Mn incorporation into
pyrite or organic phases (Huerta-Diaz and Morse, 1992; Algeo and
Maynard, 2004).
4.2.2. Cadmium and zinc
These elements are present under oxic to suboxic conditions as
soluble cations (CdCl+; Zn2+, ZnCl+; Tribovillard et al., 2004) or are
incorporated into marine plankton biomass, which is their major
carrier to the sea floor (e.g. Bruland et al., 1991). Already at very low
HS− concentrations, Cd and Zn may form sulfides (CdS, ZnS), due to
lower solubility products and faster water exchange kinetics than e.g.
Fe sulfides (Jacobs and Emerson, 1982; Rosenthal et al., 1995; Morse
and Luther, 1999; Scholz and Neumann, 2007). Indeed, in the studied
sediments, sharp Zn and Cd peaks (Fig. 5b, f) document rapid and
intensive precipitation of CdS and ZnS in weakly sulfidic bottom
waters (Morse and Luther, 1999; März et al., in press). This is
supported by SEM-EDX detection of pure idiomorphic ZnS crystals
(Fig. 10b). Above the Cd/Al and Zn/Al peaks, values decline rapidly,
most probably due to a drawdown of the respective trace metal pools
in the ambient water masses (Algeo, 2004). It is hard to estimate the
spacial extension of this drawdown, but as it is documented by our
data at both ODP Sites 1259 and 1261, this phenomenon at least
affected larger parts of the Demerara Rise continental slope. In
samples with high Zn contents, also Fe sulfides were observed which
do not contain Cd and Zn, supporting negligable incorporation of
these trace elements into pyrite (Huerta-Diaz and Morse, 1992; Scholz
and Neumann, 2007). Weak correlations of Cd/Al and Zn/Al with both
TOC/Al and S/Al at both sites (correlation coefficients of 0.01–0.36)
indicate that no significant fraction of sedimentary Cd and Zn is bound
to (sulfurized) OM or pyrite.
4.2.3. Molybdenum and nickel
These elements form soluble cations (Ni2+, NiCl+) or oxy-anions
(MoO42−) under oxic to suboxic conditions. Nickel is a micronutrient
taken up by primary producers and transported to the sea floor mainly
by OM (e.g. Bruland et al., 1991). Although conservative in ocean water
under most conditions, Mo is important for biological N fixation (e.g.
Tuit et al., 2004) and may be coupled to Mn (oxyhydr)oxides, which
then act as Mo shuttles to the sea floor under non-sulfidic conditions
(e.g. Shimmield and Price, 1986; Adelson et al., 2001; Reitz et al.,
2007). In response to algal blooms, a transport of Mo to the sea floor
via organic macromolecules forming in the water column has been
postulated (e.g. Lunau et al., 2006; Dellwig et al., 2007). In sulfidic
environments, Mo oxy-anions are transformed to particle-reactive
thiomolybdates above a certain HS− threshold (“thiomolybdate
switch”; Helz et al., 1996; Zheng et al., 2000; Adelson et al., 2001),
and scavenged from the water column by e.g. sinking OM. In sulfidic
sediments, incorporation into pyrite can be an important Mo and Ni
Fig. 10. SEM micrographs in back scatter electron mode and respective elemental spectra from representative particles. (a) Fe sulfide framboids (1–5); (b) aggregate/framboid of
idiomorphic Zn-sulfide crystals (1–4); (c) angular barite grain, probably fragment of larger diagenetic barite aggregates; (d) aggregate of fine apatite crystals (1–4), Fe sulfide with clay
coating (5). EDS spectra numbers correspond to the spot analyses of the respective numbered particles.
297
sink (Huerta-Diaz and Morse, 1992; Dellwig et al., 2002; Algeo and
Maynard, 2004). In addition, during OM sulfurization or formation of
geoporphyrins a secondary coupling of Ni and Mo to OM can be
created (e.g. Lewan and Maynard, 1982; Breit and Wanty, 1991; Algeo
and Maynard, 2004; Tribovillard et al., 2004). The distinct correlations
of Mo/Al and Ni/Al not only with TOC/Al, but also with S/Al at Sites
1259 and 1261 (Fig. 6c–f) imply that these trace metals were mainly
incorporated into (sulfurized) OM during early diagenesis. März et al.
(in press) showed that at Site 1261, only ~ 1/3 of bulk S is bound to
metal sulfides, indicating a significant contribution of sulfurized OM
to the total S pool. A close coupling of Mo to sulfurized OM was found
in several black shale deposits (Tribovillard et al., 2004; Algeo and
Lyons, 2006). In contrast, we assume that Ni was rather incorporated
into organic tissue as a micronutrient already during primary
production and is not as strongly related to OM sulfurization as Mo.
This is indicated by slightly stronger correlation of Ni/Al with TOC/Al
than with S/Al at both sites, while Mo/Al is correlated with TOC/Al and
S/Al to the same degree. The difference towards Cd and Zn is most
probably an effect of higher HS− concentrations being required for Mo
and Ni coupling to OM. These can only be reached when the initial
“buffering” of low HS− in bottom waters by CdS and ZnS formation is
declining.
4.2.4. Vanadium
Under oxic to suboxic conditions, V is present as an oxy-anion
(HVO42−, H2VO4−). Manganese (oxyhydr)oxides can play a significant
role for its transport to the sea floor (e.g. Wehrli and Stumm, 1989;
Hastings et al., 1996). Via a two-step reaction pathway, V forms
hydroxyl species (VO(OH)3−) and insoluble hydroxides (VO(OH)2)
under anoxic, and insoluble hydroxides (V(OH)3) and oxides (V2O3)
under sulfidic conditions (e.g. Breit and Wanty, 1991; Tribovillard
et al., 2004). Incorporation of V into pyrite under sulfidic conditions is
regarded as negligible (e.g. Dellwig et al., 2002; Scholz and Neumann,
2007), but V is incorporated into geoporphyrins (Lewan and Maynard,
1982; Breit and Wanty, 1991), and thus coupled to OM similar to Ni. At
Sites 1259 and 1261, the V/Al records (Fig. 5e) show patterns similar to
Cd/Al and Zn/Al, but with a more gradual decline of V/Al above the
initial peak. Increasing incorporation of V into geoporphyrins could be
responsible for keeping V/Al values relatively high, while Cd/Al and
Zn/Al rapidly declined (Breit and Wanty, 1991; Algeo and Maynard,
2004). Alternatively, bottom water V was maybe not exhausted as fast
as the Cd and Zn pools. Initial V (hydr)oxide formation was probably
limiting sedimentary Ni enrichment, as the reduction from V(IV) to V
(III) at low HS− concentrations is known to inhibit Ni incorporation
into geoporphyrins (Lewan, 1984; Breit and Wanty, 1991).
4.2.5. Iron
Under oxygen- and nitrate-free conditions, Fe (oxyhydr)oxides are
progressively reduced (Froelich et al., 1979; review by Burdige, 1993),
either chemically (e.g. Stone and Morgan, 1987; Stumm and
Sulzberger, 1992) or biologically (dissimilatory iron reduction; e.g.
Lovley, 1987; Nealson and Myers, 1992), and Fe2+ is liberated to the
surrounding (pore) water. If free HS− is present, Fe (oxyhydr)oxides are
reduced (e.g. Morse et al., 1987; Yao and Millero, 1996) and
transformed to Fe sulfides, mostly pyrite (FeS2; e.g. Berner, 1984;
Schoonen, 2004). However, if the pool of most sulfide-reactive Fe
minerals (e.g. ferrihydrite, goethite, hematite; Poulton et al., 2004) is
exhausted, HS− may start to react with fresh OM in the sediment (OM
sulfurization, natural vulcanisation; e.g. Sinninghe Damsté and de
Leeuw, 1990; Sinninghe Damsté et al., 1998). Excess HS− may also
diffuse out of the sediment, creating sulfidic conditions at the sea floor
and in the (lower) water column. Sequential Fe extraction results
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obtained in an earlier study (März et al., in press) indicated repeated
shifts from sulfidic to anoxic, non-sulfidic bottom water conditions at
Site 1261. Similar information can be obtained from the sedimentary
Fe/S ratios, available for both Sites (Fig. 8d). Periodic increases in Fe/S
ratios at Sites 1259 and 1261 indicate higher amounts of non-sulfide-
bound sedimentary Fe. Notably, Fe/S peaks do not coincide with
elevated Fe/Al values at Site 1261 (Fig. 8a), implying that these Fe/Al
peaks do not represent higher amounts of Fe oxides, but probably
formation of syngenetic pyrite in a sulfidic water column. Co-
occurrence of Fe/S peaks with lowest–but compared to AS still
enriched–trace element/Al, lowest TOC/Al, and highest P/Al values
points to less reducing, but still anoxic conditions. High Fe/S and Fe/Al
ratios within the GH are probably a combined effect of elevated Fe-
oxide (6–35% of total P bound to Fe-oxides) and glauconite (containing
~ 20% Fe) contents. As stated above, März et al. (in press) found that
only about 15–35% of bulk S at Site 1261 are bound to pyrite (see also
Böttcher et al., 2006), indicating that sulfurized OM may be a major S
carrier in these black shales.
4.2.6. Phosphorus
In the ocean, P is mainly present as HPO42−, which is not redox-
sensitive itself, but strongly coupled to the cycles of Fe and OM. Fresh
iron (oxyhydr)oxides cannot only adsorb large amounts of phosphate
ions, but phosphate may also be co-precipitated during Fe (oxyhydr)
oxide formation. Thus, Fe (oxyhydr)oxides can play a major role in the
transport of P to the sea floor under oxic conditions (e.g. Feely et al.,
1990; Slomp et al., 1996; Poulton and Canfield, 2006). Another P
carrier to the sea floor is marine OM, as marine phytoplankton
contains a relatively well-defined amount of P (mean C/P ratio of
106:1; Redfield, 1958). Under reducing conditions, a gradual decou-
pling of P from both the Fe and the OM cycles takes place: Dissolution
of Fe (oxyhydr)oxides liberates phosphate to the surrounding water.
Furthermore, under anoxic conditions there is a preferential regen-
eration of organic P from OM in relation to organic carbon (e.g. Ingall
et al., 1993; Ingall and Jahnke, 1997), resulting in low P burial
capacities of anoxic sediments and C/P ratios of N106 (e.g. Anderson
et al., 2001; review by Algeo and Ingall, 2007). Our bulk sediment P
data indicate P depletion over large parts of the investigated intervals,
resulting in high C/P and low P/Al ratios (Fig. 8b, c). This implies a very
effective regeneration of both Fe (oxyhydr)oxide- and OM-bound P
from the sediment under anoxic, probably even sulfidic bottom water
conditions. However, P/Al enrichments at both sites, with very low C/P
ratios and Fe-bound P as one of the major fractions (Figs. 8b, c and 9),
document conditions favorable for P burial, and even (partial)
preservation of Fe-oxides (and the Fe–P coupling), in the sediment.
Partial transfer of Fe-bound P, and nearly complete transfer of OM-
bound P, to authigenic apatite is consistent with the “sink switching”
hypothesis, i.e. P transfer from rather labile binding forms into
authigenic apatite as the ultimate oceanic P sink (e.g. Delaney, 1998;
Filippelli, 2001). The high P content of the GH is probably a mixed
signal of originally larger amounts of Fe oxide-bound P transformed to
the now dominant authigenic CFA, and input of older, well-crystal-
lized authigenic and/or detrital apatite (Fig. 9b). The fact that apatite
grains identified under the SEM in GH samples are often rounded
(Fig. 10d) points to re-deposition, e.g. by bottom currents.
4.3. Geochemistry at sites 1259 and 1261 — similarities and differences
Comparing quasi age-equivalent records from the two drill sites on
Demerara Rise in terms of a paleo-water depth transect bears a
fundamental complication. Cretaceous water depths were most
probably different than today due to subsidence and tilting of the
Demerara Rise during progressive rifting in the South Atlantic since
the earliest Cretaceous (Erbacher et al., 2004). In this context, Erbacher
et al. (2005) stated that transgressive Cretaceous black shale
deposition at Site 1259 started later than at all other ODP Leg 207
sites (including Site 1261, where black shales started to develop before
the OAE2), implying that during the Cretaceous Site 1259 was situated
in shallower water depths than Site 1261. Benthic foraminiferal
assemblages also support that re-oxygenation of the Demerara Rise
sea floor occurred first at Site 1259 followed by the other ODP Leg 207
sites (Friedrich and Erbacher, 2006).
4.3.1. Sediment source
From the high-resolution profiles presented in this study, it
appears that the cyclicity of the carbonate, Al and TOC/Al records,
and thus the overall sedimentary input is much more regular at Site
1261 compared to Site 1259. Based on Al and carbonate data, we infer
that variable dilution by marine carbonate was the main process
leading to the observed fluctuations in carbonate, Al and probably
TOC/Al. Well-preserved mm-scale lamination at Site 1261 excludes
physical and biological disturbance of the sediment in the investigated
interval. The strong correlation between all terrigenous “marker
elements” such as Al, K, Mg, Ti and Zr (Fig. 4a–e) implies a stable
detrital source area at Site 1261. “Terrestrial” elements (Fe, K, Mg, Ti,
Zr) normalized to Al support that the lithology of the detrital source
material is close to AS composition (Fig. 7), consistent with the
findings of Hetzel et al. (2006). At Site 1259, however, the terrestrial-
sourced elements are overall slightly more enriched than at Site 1261
(Table 2; Fig. 7), implying a stronger detrital influence, and thus a
more proximal location of Site 1259 during the Coniacian–Santonian
consistent with Erbacher et al. (2005) and Friedrich and Erbacher
(2006). Alternatively, the input of marine biogenic carbonate could
have been lower at Site 1259. Weaker carbonate-Al anti-correlation,
weaker correlations of the detrital elements and cyclic Zr/Al variations
support that the interplay of marine versus terrigenous dilution was
disrupted by mass wasting, winnowing of fine particles, and/or
varying sources of lithogenic input. The periodic, potentially erosional
activity of winnowing bottom currents would also offer an explana-
tion for lower sedimentation rates at Site 1259 than at Site 1261,
where continuous hemipelagic sedimentation is documented. The
occurrence of glauconitic horizons, as observed at Site 1259, is
interpreted by Friedrich and Erbacher (2006) and Nederbragt et al.
(2007) as an indication for extremely low sedimentation rates,
possibly periodic erosion due to increased bottom currents at Site
1259. Indeed, coarser grain size, enrichment of heavy mineral-bound
Zr (Fig. 3d), association of glauconite and detrital apatite (identified by
sequential P extraction and SEM analysis; Figs. 9a and 10d), and low
carbonate contents within the GH support this conclusion. Still,
enrichments of K/Al, Mg/Al, and depletion of Ti/Al are no typical
features of a winnowing horizon, but rather suggest an import of
detrital material from a different source area with a K- and Mg-richer,
and Ti-poorer lithology. Unfortunately we cannot be more precise in
that respect due to limited knowledge about the detrital source area or
related drainage systems to Demerara Rise.
4.3.2. Redox cycles
Rapid and cyclic bottom water redox fluctuations at Site 1261 were
suggested to document variations between sulfidic and anoxic, non-
sulfidic conditions in an earlier work of März et al. (in press).
Comparing the records of Cd/Al, Mo/Al, Ni/Al, V/Al and Zn/Al at Site
1261 and the part of 1259 above the GH, the variations from maxima
to minima (Fig. 5b–f) and the respective trace element EFs (Fig. 7) are
similar at both sites, despite lower time resolution at Site 1259. This
indicates that at least the upper part of Site 1259 (499.60–500.10 mcd)
experienced similar redox variations as Site 1261. Detection of
variable, but overall anoxic conditions not only at the supposedly
shallower Site 1259, but also at the deeper Site 1261 suggests that
indeed large parts of the continental margin at Demerara Rise were
affected by bottom water anoxia during OAE3. However, more detailed
comparison of redox-sensitive proxy records reveals slight differences
between both sites. Compared to the four nearly identical redox cycles
 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301
at Site 1261 (regular cyclicity, very similar maximum and minimum
element/Al values in each cycle, repetitive “sawtooth” patterns), Site
1259 displays more irregular variations, with some element/Al
minima (500.15–500.22 mcd; Fig. 5b–f) and maxima (499.92–
499.98 mcd; Fig. 5b–f) that are less pronounced than expected.
Thus, we conclude that although redox cyclicity at Site 1259 above the
GH was similar to Site 1261, the intensity of anoxia/euxinia and the
regularity of redox changes were less pronounced. A major difference
between both sites is the occurrence of the glauconite horizon at Site
1259 (dotted bar, Figs. 2, 3, 5, 8). The relatively low Al ratios of Cd, Ni,
Mo, V and Zn throughout the GH (Fig. 5b–f), in combination with
lower TOC/Al (Fig. 2b) and high Fe/S (Fig. 8d) ratios point to less
reducing conditions during its deposition than during the overlying
section of Site 1259. In support of this, the P/Al and C/P records within
the GH show highest (0.6–3.3) respectively lowest (0.3–2.9) values of
all samples (Fig. 8b, c), proving enhanced P retention in the sediment
under at least non-sulfidic conditions. In addition, ~ 20% of all P
measured in the GH is Fe oxide-associated (Fig. 9a). We assume that
depositional conditions during formation of the GH were probably
influenced by enhanced bottom current activity, introducing less
reducing bottom waters and winnowing fine particles.
The sediment section below the GH at Site 1259 (below
500.48 mcd) is the only interval where Mn/Al reaches values
comparable to AS (Fig. 5a). This Mn/Al maximum is paralleled by
highest overall carbonate contents of up to ~100 wt.% (Fig. 2c). As
discussed earlier, Mn carbonate formation requires elevated Mn2+
levels in the pore water, which are induced by reductive dissolution of
Mn (oxyhydr)oxides. Deposition of Mn (oxyhydr)oxides requires
periodically oxic bottom water conditions. Indeed, less reducing
bottom water conditions are implied by relatively low Cd/Al and Zn/
Al ratios (Fig. 5b, f). Also low C/P ratios indicate P burial in the sediment
under oxic conditions (Fig. 8c). However, V/Al and especially Mo/Al and
Ni/Al exhibit very high values (Fig. 5c–e), opposing oxic conditions.
Notably, the trace elements highly enriched below the GH are those
associated to OM (which is in support of the high TOC/Al values in the
respective interval), while sulfide-bound Cd and Zn are relatively low.
Despite these two contradictory interpretations for the interval below
the GH, its redox development did obviously not follow the regular
systematics as the redox cycles above the GH and the ones at Site 1261.
4.3.3. Comparison with OAE2 at Demerara Rise
Comparison of OAE3 deposits from Sites 1259 and 1261 with
values reported for the OAE2 (Cenomanian–Turonian) at Demerara
Rise (Brumsack, 2006; Table 2; Fig. 7) shows very similar EFs for most
trace elements. A direct comparison of OAE3 high-frequency redox
cycles is hampered by the lack of high-resolution records for OAE2.
However, a geochemical study of sediments deposited before, during
and after OAE2 at ODP Sites 1258 and 1260 (Hetzel et al., 2009)
allows some comparison of geochemical processes occurring at
Demerara Rise during both OAEs.
Similar to OAE3, Hetzel et al. (2009) state that organic matter is
an important carrier of S in OAE2 deposits at Demerara Rise, which is
due to low input of sulfide-reactive iron to the sedimentary system.
Also Böttcher et al. (2006) found similar Fe–S systematics in OAE2
black shales at Demerara Rise, indicating an Fe-limited system, a high
degree of pyritization and intensive OM sulfurization. Obviously,
detrital iron delivery to Demerara Rise was low during both OAEs,
while HS− production was comparably high.
Manganese is generally depleted in sediments from both OAEs as
well (Figs. 5a, 7), which is attributed to its reductive leaching from the
sediment under anoxic conditions and removal in an open-margin
oxygen minimum zone. Intervals with relatively elevated Mn/Al
values occur only in association with very carbonate-rich layers during
both OAEs, which is not necessarily associated with oxidation events,
but might also be related to diagenetic formation of carbonate layers
or sediment layers with reduced porosity (Hetzel et al., 2009).
299
During OAE2, Hetzel et al. (2009) find a significant depletion of
Zn (with mean Zn/Al values of ~ 50 ⁎ 10− 4 and ~155 ⁎ 10− 4 at Sites 1258
and 1260, respectively) compared to the under- and overlying
sediments. This is in contrast with the variable, but generally elevated
Zn/Al values during the studied OAE3 interval (mean Zn/Al values of
~380 ⁎ 10− 4 and ~ 335 ⁎ 10− 4 at Sites 1259 and 1261, respectively;
Fig. 5f). However, we observe repeated intervals with lower Zn/Al
values, comparable to the mean OAE2 values of Hetzel et al. (2009).
As most probable explanation for these unexpected low Zn/Al in black
shales, Hetzel et al. (2009) state a global drawdown of the Zn sea water
pool, resulting from extreme and wide-spread ocean anoxia to euxinia
and subsequent syn- or diagenetic ZnS formation. This hypothesis is
consistent with the model of März et al. (in press), where repeated
establishment of weakly sulfidic bottom water conditions leads to
rapid precipitation of CdS and ZnS (Fig. 5b, f), followed by (at least
local) drawdown of the Cd and Zn sea water inventories. We therefore
suggest that similar processes of trace metal drawdown were active
during both OAE2 and 3. Still, while having a global impact on oceanic
trace metal budgets during OAE2, their effects were less persistant
during OAE3 and probably restricted to extreme environments like
Demerara Rise. This interpretation is consistent with the C and N
isotope data of Junium and Arthur (2007). They assume similar
geochemical conditions in the water column during both OAEs, yet
describe OAE2 as a global anoxic event, while OAE3 affected the global
carbon and nitrogen cycles only locally.
5. Conclusion
During Coniacian–Santonian time ODP Sites 1261 and 1259 were
dominated by marine (calcareous and opal) sedimentation and burial
of large amounts of OM, which at least partly related to elevated OM
preservation by diagenetic OM sulfurization. The presented new
geochemical data support the conclusion that both sites were affected
by similar bottom water redox conditions throughout the investigated
intervals, which were generally anoxic, and even sulfidic for prolonged
periods. However, bottom water and sediment redox were subject to
relatively rapid and cyclic variations, which occurred at both sites. This
observation suggests that prevailing redox conditions affected large
parts of the continental margin at Demerara Rise during OAE3. The
sedimentary record documents that redox fluctuations were regular
in frequency and degree of changes at the deeper Site 1261. At the
shallower position of Site 1259 sedimentation instead was stronger
affected by variations in detrital supply and/or winnowing of bottom
currents, and probably periodic erosion, together supporting a more
proximal location. In contrast, steady hemipelagic sedimentation
prevailed at Site 1261, consistent with a greater water depth.
Especially during the formation of the glauconitic horizon at Site
1259, the depositional regime was physically disturbed, and bottom
waters were most probably better oxygenated. Speciation of P
indicates that at both sites Fe oxide-bound P and authigenic apatite
are the dominant sedimentary P species, while detrital apatite seems
to be of higher importance within the GH. Only minor P contributions
are related to fish bones and organic P. Geochemically, the studied
OAE3 deposits are well-comparable to the OAE2 black shales from
Demerara Rise, indicating that both anoxic events created very similar
paleoenvironmental conditions at this location, although the impact
of OAE3 on marine biogeochemical cycles was probably rather local.
Acknowledgements
We thank W. Hale for sampling assistance, and B. Kockisch, S. Pape,
S. Siemer and K. Enneking for analytical and logistic support. Help of K.
Küster, J. Hoffmann and N. Allroggen with the phosphate extraction is
highly appreciated. Electron microscopy was performed at the EMU
(Utrecht University), and we thank M. Drury for his support. CM
thanks G. de Lange and the Geochemistry group at Utrecht University
300 C. März et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 286–301
for great hospitality during his research stay. TW acknowledges the
Royal Society-Wolfson Research Merit Award. This study was funded
by the DFG via the International Graduate College EUROPROX. The
manuscript benefited significantly from constructive comments of A.
Negri and two anonymous reviewers.
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Paleo-redox conditions during OAE 2 reflected in Demerara Rise sediment

geochemistry (ODP Leg 207)
Almut Hetzel a,⁎, Michael E. Böttcher b,c, Ulrich G. Wortmann d, Hans-Jürgen Brumsack a
a
Institute for Chemistry and Biology of the Marine Environment (ICBM), Carl von Ossietzky University, P.O. Box 2503, D-26111 Oldenburg, Germany
b
Max Planck Institute for Marine Microbiology, Celsiusstrasse 1, D-28359 Bremen, Germany
c
Leibniz Institute for Baltic Sea Research Warnemünde, Seestrasse 15, D-18119 Warnemünde, Germany
d
Department of Geology, University of Toronto, 22 Russel street, Ontario, Canada M5S 3B1

a r t i c l e i n f o a b s t r a c t

Article history: Cretaceous black shales deposited under severe oxygen-depletion are carriers of proxy signals for paleoenviron-
Received 1 December 2007 mental conditions. Using high-resolution patterns of iron and sulfur speciation, stable sulfur isotope
Received in revised form 8 August 2008 discrimination, and trace element enrichment from black shale sequences of Sites 1258 and 1260 we identified
Accepted 3 November 2008
alterations of the depositional environment during the Cenomanian/Turonian boundary Event (OAE 2) in the
southern North Atlantic (ODP Leg 207, Demerara Rise).
Keywords:
Demerara Rise
Changes in redox-conditions are suggested by high ratios of reactive to total iron which indicate that pyrite was
Ocean Drilling Program formed both in the water column and within the sediment. This corresponds to euxinic paleoenvironmental
Leg 207 conditions with at least temporarily free dissolved sulfide in the water column, a situation similar to the modern
Trace metals deep Black Sea. In addition, besides fixation of sulfide as iron sulfide, organic matter acted as an important sulfur
Oceanic Anoxic Event 2 trap during early diagenesis. Stable sulfur isotope fractionation went through a minimum within the OAE 2 interval
CTBE indicating enhanced sulfur isotope discrimination during highest burial of organic matter (OM) potentially due to
Paleoenvironment lower burial efficiency of reduced sulfur and/or a higher contributions from the oxidative part of the sulfur cycle
Pyrite
(e.g., in the water column or the surface sediments). Elevated Fe/Al and Co/Al values within the Cenomanian/
Sulfur isotopes
Turonian interval confirm euxinic conditions but, at the same time, require a zone where reducing but non-sulfidic
conditions prevail, allowing reductive Fe and Co mobilization in oxygen-depleted nearshore sediments. The
existence of an expanded oxygen-minimum-zone (OMZ) is demonstrated by extremely low Mn/Al ratios.
A change in the trace metal (TM) inventory of seawater is postulated from a decline in seawater derived TM
enrichment. Because hypoxic or even euxinic environments form an important sink for TM, the enlargement of
euxinic depositional areas at the global onset of black shale deposition during OAE 2 have likely led to a drawdown
of the seawater TM reservoir.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction characterized by a global organic carbon burial episode leading to a

In the mid-Cretaceous, several distinct periods of organic-rich black
shale deposition appear. The enhanced burial of organic carbon in
marine sediments during these so called Oceanic Anoxic Events (OAEs;
Schlanger and Jenkyns, 1976) is thought to arise either from enhanced
bio-productivity or from intensified preservation of organic matter
during anoxic conditions (e.g., Arthur et al., 1987, 1988; Schlanger et al.,
1987). The Cenomanian–Turonian Boundary Event (CTBE = OAE 2; ca.
93.5 Ma) is one of the best studied global Oceanic Anoxic Events. It is
⁎ Corresponding author.
E-mail addresses: almut.hetzel@gmx.de (A. Hetzel),
michael.boettcher@io-warnemuende.de (M.E. Böttcher), brumsack@icbm.de
(H.-J. Brumsack).
positive shift in δ13C values of organic carbon and carbonate (e.g.,
Schlanger et al., 1987; Arthur et al., 1988; Gale et al.,1993; Erbacher et al.,
2005). As the carbon cycle is tightly coupled to the sulfur cycle, pertur-
bations in the global carbon cycle lead to changes in the seawater sulfur
isotopic composition (e.g., Strauss, 1999; Paytan et al., 2004; Wortmann
and Chernyavsky, 2007).
During Ocean Drilling Program (ODP) Leg 207, relatively expanded,
shallowly buried Cretaceous sediments were recovered from Demer-
ara Rise off Suriname, South America. CTBE black shales on Demerara
Rise form part of a thick black shale succession encompassing the
Albian to Santonian (Shipboard Scientific Party, 2004). This may be the
result of both the paleogeographic setting of Demerara Rise (lacking
significant ventilation of bottom-waters prior to the opening of the
equatorial Atlantic gateway, which may have taken place in the
Campanian; see Friedrich and Erbacher, 2006) and enhanced nutrient
influx. The latter may have been evoked by terrestrial runoff and/or

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.11.005
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328
upwelling due to the proximal position of Demerara Rise to the South
American landmass.
Cretaceous black shales deposited under severe oxygen-depletion
are carriers of proxy signals for paleoenvironmental conditions like
varying levels of bottom water dysoxia and/or enhanced surface water
productivity. Changes in water column redox conditions lead to re-
sponses in the coupled biogeochemical sulfur–carbon–metal cycles and
associated sedimentary signal formation. Therefore, distribution pat-
terns of iron and sulfur speciation, sulfur isotope partitioning, and
enrichments of redox-sensitive and sulfide forming trace metals provide
important paleoenvironmental information on dynamics of biogeo-
chemical element cycles and corresponding water column redox-
conditions during black shale deposition. Excess iron contribution to
selected Cretaceous Leg 207 black shales due to pyrite formation in a
euxinic water column was shown by iron and sulfur speciation analyses,
and enhanced organic matter sulfurization was shown to be caused by a
limitation of reactive iron to form sulfide minerals (Böttcher et al., 2006).
High enrichments of redox-sensitive elements in organic carbon-
rich sediments have been related to anoxic bottom waters. Under
reducing conditions these metals may either be precipitated as
sulfides, co-precipitated with iron sulfides or bound to organic matter
(Brumsack, 1980; Jacobs et al., 1985, 1987; Brumsack, 1989; Breit and
Wanty, 1991; Hatch and Leventhal, 1992; Calvert and Pedersen, 1993;
Piper, 1994; Nijenhuis et al., 1998). Based on the specific trace metal
patterns of coastal upwelling areas and euxinic settings Brumsack
(2006) discussed the enrichment of trace metals in Cretaceous black
shales attempting to ascertain whether enhanced bio-productivity or
widespread stagnation triggered black shale formation.
In the present study, we report on a high-resolution geochemical
tracer record for black shale sequences of ODP Leg 207 Sites 1258 and 1260
using distribution patterns of trace element enrichment, iron and sulfur
speciation, and stable sulfur isotope discrimination to identify changes in
redox-conditions of the depositional environment during OAE 2.
Fig. 1. Geographic position of Sites 1257–1261 at Demerara Rise (ODP Leg 207). (Online Map Creation www.aquarius.geomar.de).
303
2. Material and methods
2.1. Site description
During ODP Leg 207, sediment cores were drilled on the Demerara
Rise in the tropical North Atlantic (Fig. 1). The rise stretches ca. 380 km
along the coast off Suriname and reaches a width of ca. 220 km from the
shelf break to the northeastern escarpment, where water depths increase
sharply from 1000 to more than 4500 m. While most of the plateau lies in
shallow water (700 m), the northwest margin forms a gentle ramp
reaching water depths of 3000 to 4000 m. The five drill sites (Sites 1257–
1261) constitute a depth transect with water depths ranging from
1900 to 3200 m located within a tropical oxygen minimum zone that
caused deposition of laminated organic-rich sediments of latest Albian to
earliest Campanian age. Upper Cenomanian to Lower Turonian sedi-
ments on Demerara Rise are mainly expressed by distinctly laminated
black shales with well-preserved fish debris and phosphatic nodules.
Within this black shale sequence light-colored, laminated foraminiferal
packstones and wackestones occur (Shipboard Scientific Party, 2004). A
detailed sedimentological description is given by Erbacher et al. (2004).
Linear sedimentation rates (LSRs) were estimated by the Shipboard
Scientific Party (2004) from age-depth plots by fitting curves to available
biostratigraphic and paleomagnetic data over certain depth intervals.
Poor preservation or even absence of microfossils and the ambiguous
interpretation of paleomagnetic data limit the bio- and magnetostrati-
graphic age assignment in most of the black shale sequences (Cenomanian–
Santonian). Therefore, LSRs calculated for these intervals (0.3–0.5 cm/ka
at Sites 1257, 1258, and 1259 and slightly higher values of ~0.85 cm/ka at
Sites 1260 and 1261) should be considered as imprecise estimates.
Stable isotope stratigraphy provided by Erbacher et al. (2005)
allows a detailed correlation of the investigated sites through the OAE
2 interval. At all studied sites, a distinctive positive carbon isotope
excursion (~6.5‰) of the OAE 2 was identified (Fig. 2). The same authors
304 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

Fig. 2. Depth-profiles for TOC contents for the whole sediment column investigated (open circles) (Hetzel et al., 2006) and for Cenomanian/Turonian black shales at Demerara Rise,
ODP Sites 1258 and 1260. Grey: OAE 2; δ13Corg-curve after Erbacher et al. (2005).

were able to correlate a number of short-termed δ13Corg peaks and at Site 1260). (3) An interval “C” with δ13Corg values rising to −23 and
troughs within and above the excursion interval between the −21‰. (4) The final maximum value “D”. (5) A short positive peak “E”
investigated sites. The events of this record include: (1) The onset of occurs during the general decrease in isotope values (not present at Site
the excursion labeled “A”. (2) A short-termed minimum “B” (not present 1258). In addition, Erbacher et al. (2005) also correlated two peaks (“F”
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328
and “G”) located above the OAE 2 between the sites. Assuming a duration
of ~400 ka for the interval between “A” (onset of excursion) and “D” (end
of plateau) Erbacher et al. (2005) calculated average sedimentation rates
between ~0.25 cm/ka (Site 1260) and ~1 cm/ka (Site 1258) for the OAE 2.
There is no more detailed information available about sedimentation
rates for the intervals above and below OAE 2 or variations within this
interval.
In this study, two ODP sites along the Demerara Rise paleodepth-
transect (Sites 1258 and 1260, see Table 1) were chosen to reconstruct
paleoenvironmental changes during the late Cenomanian to earliest
Turonian black shale deposition interval. Depths are expressed in meters
composite depth (mcd), following the shipboard splice between the
different holes drilled at each site (Shipboard Scientific Party, 2004).
2.1.1. ODP Site 1258
Site 1258 is located in a water-depth of 3192.2 m below modern sea
level (mbsl) on the gently dipping western slope (~2°) of Demerara Rise. It
is the deepest location in the SE–NW paleoceanographic depth transect
across Demerara Rise (Shipboard Scientific Party, 2004). The 4 m-thick
OAE 2, as defined by the pronounced δ13Corg excursion, is located at a
depth of 426–422 mcd (Erbacher et al., 2005). Based on δ13Corg measure-
ments, Erbacher et al. (2005) described a hiatus in the uppermost part of the
OAE. The sediments of the investigated section comprise finely-laminated
dark shales with occasional beds of phosphatic nodules, stringers of
very dark homogeneous shales, and rare concretionary limestone nodules.
Thirty-three and a half meters (415–448.5 mcd, see Table 2) of upper
Cenomanian to lowermost Turonian laminated black shale sediments
were investigated from a spliced interval of Holes 1258A, 1258B, and
1258C. 845 samples were taken at 1 cm resolution for the OAE 2 interval
and at ~10 cm in underlying sediments. Assuming a sedimentation rate of
~1 cm/ka the studied interval covers a time span of ~3.35 Ma of deposition.
2.1.2. ODP Site 1260
Site 1260, in a water-depth of 2548.8 mbsl, is positioned on the gently
dipping (~1°) northwest-facing slope of Demerara Rise, at an inter-
mediate depth in the SE–NW paleoceanographic depth transect. The
1.4 m thick OAE 2 is located between 426.4 and 425.0 mcd, being thus
much thinner than at Site 1258. Lithologically, the interval is very similar
to Site 1258, although phosphatic nodules are not as common as at the
deeper site (Erbacher et al., 2005). About 8.5 m of upper Cenomanian to
lowermost Turonian laminated black shale sediments were sampled
every ~5 cm (219 samples in total, see Table 2) from a spliced interval of
Holes 1260A and 1260B. Sedimentation rates of the OAE 2 interval are
estimated to be on the order of approximately 0.25 cm/ka, thus leading
to the same duration of ~3.4 Ma of deposition for the studied sequence.
2.2. Analytical methods
Sediments splits were freeze-dried, ground and homogenized in an
agate ball mill. For X-ray fluorescence (XRF) analysis (Philips® PW 2400
X-ray spectrometer), 600 mg of sample powder were mixed with
3600 mg of a 1:1 mixture of dilithiumtetraborate (Li2B4O7) and lithium-
metaborate (LiBO2), or with 100% dilithiumtetraborate for carbonate-
rich samples, preoxidized at 500 °C with NH4NO3 (p.a.) and fused to glass
beads. Total sulfur (ST) and total carbon (TC) were analyzed using an
Table 1
Drilling locations Site 1258 and 1260, ODP Leg 207
Site Hole Latitude Longitude Water depth OAE 2 interval
(mbsl) (mcd)
1258 A 9° 26.000′N 54° 43.999′W 3192.2 425.95–422.18
1258 B 9° 26.000′N 54° 43.982′W 3192.2
1258 C 9° 26.000′N 54° 43.966′W 3192.2
1260 A 9° 15.984′N 54° 32.633′W 2548.8 426.34–424.94
1260 B 9° 15.931′N 54° 32.652′W 2548.8
mbsl = meters below sea level; mcd = meters composite depth; SR = sedimentation rate.
305
Table 2
Sampling Site 1258 and 1260
Site Sampled Number of Time of Sampling Sampling
interval samples deposition resolution resolution
(mcd) (Ma) (cm) (ka)
1258 415.0–448.5 845 ~ 3.35 ~ 1/~ 10 ~ 1/~ 10
1260 423.5–432.0 219 ~ 3.40 ~5 ~ 20
mcd = meters composite depth.
ELTRA® CS-500 IR-analyzer. Total inorganic carbon (TIC) was determined
coulometrically by a UIC® CM 5012 CO2 coulometer coupled to a CM 5130
acidification module. Total organic carbon (TOC) was calculated as the
difference between TC and TIC. Procedures and accuracy of the methods
were checked with in-house reference materials (Prakash Babu et al.,
1999; see Appendix A). Different sedimentary sulfur fractions, chromium-
reducible sulfur (SP, essentially pyrite), organic matter (essentially
kerogen-bound organic sulfur, SORG) and acid volatile sulfur (SAVS) were
separated quantitatively from powdered freeze-dried samples, as
described by Böttcher et al. (2006). Chromium reducible sulfur, essentially
pyrite sulfur, SP, was extracted for 2 h via hot acidic Cr(II)Cl2 (Zhabina and
Volkov, 1978; Canfield et al., 1986; Fossing and Jørgensen, 1989). Liberated
H2S was precipitated quantitatively in Zn acetate traps and measured
spectrophotometrically (Cline, 1969). The organic sulfur fraction, SORG,
was calculated as the difference of total sulfur and the sum of chromium-
reducible sulfur (Böttcher et al., 2006). SAVS was extracted from selected
samples from Site 1258 via anaerobic distillation with 6 M HCl (1 h). Since
FeS is not expected in the black shale samples to survive the diagene-
tic pyritization and lab-based freeze-drying process, the SAVS fraction is
assumed to correspond to acid-volatile metal monosulfides. ZnS, for
instance, that might have been formed in a euxinic water column, has
been found in C/T samples in the present study via SEM-EDX, and has also
been reported in Cretaceous black shales previously (Brumsack, 1980).
ZnS would have survived burial and later sample handling.
The amount of pyrite iron (FeP) was calculated from the SP content
assuming ideal stoichiometry. This fraction essentially represents the total
highly reactive iron fraction (Raiswell and Canfield, 1998; Poulton and
Raiswell, 2002). To confirm this approach, iron-oxide bound iron was
separately determined in selected black shale samples from Sites 1258 and
1260 and presented by Böttcher et al. (2006). As described in detail by
these authors, iron(oxyhydr)oxide phases were extracted from sediment
samples using a buffered solution of Na dithionite and extracted iron was
determined spectrophotometrically. It was found that this fraction is only
present in very small amounts and that pyrite iron amounts to 96–99% of
the total highly reactive iron pool. For samples from Site 1258 34S/32S ratios
of the SP bound sulfur were determined by means of C-irmMS using a
Eurovector 3000 elemental analyzer (EA) coupled to a Thermo Finnigan
MAT253 and are given in the δ-notation versus the international V-CDT
standard. Calibration of the mass spectrometer was carried using interna-
tional IAEA and NBS reference materials. Sulfur isotope results for Site 1260
will be presented in a separate communication (Böttcher et al., in prep.).
Finally, selected non-ground carbon-coated (BAL-TEC sputter-coating
device SCD 005) freeze-dried sediment samples were investigated by
means of energy-dispersive X-ray analysis on an Oxford Link ISIS 300
EDX-System with Pentafet S ATW Si-detector installed on a Zeiss DSM
940 scanning electron microscope (SEM).
3. Results and discussion
3.1. Preliminary remarks
SR
(cm/ka)
To account for dilution effects by varying carbonate or organic matter
~1
contents trace element contents were normalized to Al (TE/Al ratio). In
cases of very low Al contents (see Figs. 3 and 4), normalization may lead
~ 0.25 to exaggerated peaks in TE/Al ratios, which has to be kept in mind when
interpreting TE/Al profiles (van der Weijden, 2002). Some elements, like
Al, Ti, K, Rb and Zr, are only present in the detrital component and are not
306 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328
influenced either by biogenic or diagenetic processes. Significant
variations in TE/Al ratios of these elements therefore reveal changes in
source area composition. While most of the investigated sediment
intervals show TE/Al ratios similar to average shale (AS; Wedepohl, 1971,
1991), several sediment layers of one centimeter to several decimeters
thickness were identified by characteristic TE/Al ratios. At Site 1260 a
35 cm thick interval (425.61–425.96 mcd) within the OAE 2 is
characterized by low K/Al (0.07, AS = 0.34), high Ti/Al ratios (0.102,
AS = 0.053) and is depleted in Si (Si/Al 2.58, AS = 3.11; see Appendix B).
From macroscopic observation (Appendix B-b), this interval most likely
is a diagenetically altered ash bed. At Site 1258, three sediment layers
within OAE 2 (423.51–423.53 mcd, 423.87–424.04 mcd, and 425.22–
425.50 mcd) correspond to this layer, identified by similar disturbances
in TE/Al profiles. At both sites abrupt changes in carbonate, TOC and TS
contents from extremely high concentrations to near zero values can be
identified. Light δ13C values of the carbonate in the discussed interval at
Site 1260 (Friedrich, pers. communication) point towards the involve-
ment of microbiological processes like anaerobic oxidation of methane
(AOM) (e.g., Galimov, 2006). The production of bicarbonate by AOM
could result in the precipitation of authigenic carbonates, and thus
increase the degree of carbonate diagenesis implying recrystalization of
carbonates from foraminifera and nanofossils (Erbacher et al., 2004).
With the geochemical methods applied (bulk element concentrations)
the origin of the material can not be identified. To avoid misinterpreta-
tion of changes in element distribution patterns, samples from these
intervals (7 samples from Site 1260 and 27 samples from Site 1258) were
excluded from following discussion regarding changes of redox-
conditions and trace metal availability. As the bulk geochemistry of
sites is similar, analytical results of discussed intervals are given as
average values listed in Appendix B-c.
3.2. Bulk parameters
Fig. 2 shows the depth profiles of total organic carbon (TOC) for the
whole sediment column (data from Hetzel et al., 2006) and the upper
Cenomanian to lower Turonian black shale sequences (C/T back
shales), which are in the focus of this study.
Sediments above these sequences are characterized by low TOC
contents (b0.4%). Below these intervals TOC contents decrease from
~ 10% to ~1% with increasing depth. The C/T black shales show varying
TOC values: lowest contents (almost 0%) in carbonate-rich layers and
highest contents (30.2% at Site 1258 and 23.1% at Site 1260) within the
OAE 2 interval, which is identified by correlation with the δ13Corg
curve from Erbacher et al. (2005) and marked in grey.
Figs. 3 and 4 show the bulk chemistry of the C/T black shales: as
mentioned above, highly variable TIC contents (b0.2–11.8%) lead to
dilution effects, which are shown by the inverse distribution pattern
for TIC and Al, representing terrigenous detritus. The TIC profiles
display the light–dark cycles described by the Shipboard Scientific
Party. Whereas the profile of Site 1260 suggests a regular cyclicity
possible modulated by orbital forcing, carbonate contents of Site 1258
show a less regular distribution pattern despite higher resolution (see
Table 2). For both sites, time series analysis of our high-resolution TIC
data does not evidence orbital cyclicity.
Nederbragt et al. (2007) analyzed the cyclicity during the Mid-
Cretaceous at Demerara Rise. Due to the irregular spacing of the
carbonate-rich and organic-rich cycles (lack of precise age control,
variable sedimentation rates and/or degree of compaction and minor
hiatuses), the authors concluded instead of establishing a continuous
cyclostratigraphy for the entire organic-rich unit to perform time series
analysis of sediment color data in selected intervals in combination with
thin section analysis of representative lithologies. They found that cyclic
variation in lithology at Demerara Rise is inferred to represent eccentricity
and precession cycles with a weak obliquity component. For analysis of
the cyclicity during OAE 2 the authors examined two cores from Site 1258
and 1260. Both, precession and eccentricity cycles were found.
To better compare TOC and ST contents for Demerara C/T black shales
with other C/T sections we calculated TOCcf and ST cf for a carbonate-free
sediment. Profiles are given in Figs. 3 and 4 beside profiles of absolute
concentrations. For Site 1258 most of the TOC values vary between ~0.5
and ~15%. Adjusting for dilution by carbonate resulting TOCcf values are
quite higher (~10–~25%). Some intervals of half a meter thickness are
characterized by TOC contents N20%. These peaks are distributed right
below, within and above OAE 2. For Site 1260 the TOC contents vary
between ~0.5 and ~12% and on a carbonate free basis TOCcf values fall
between ~15 and ~22%. Highest TOC contents (N15%) are found within
OAE 2.
Average contents below, within and above OAE 2 (Table 3) show
higher TOC and lower TIC contents for Site 1258 in comparison to Site
1260. For both sites, average TOC values are in the same range (TOC:
6.9–10.1%; TOCcf: 17.6–19.3%) below and above the OAE 2 and slightly
higher during the OAE 2 with 17.8% (TOCcf 22.4%) at Site 1258 and 12.1%
(TOCcf 22.8%) at Site 1260. The same is true for ST values with 1.5–2.4%
(ST cf 3.8–4.7%) below and above and 5.0% (ST cf 6.3%) within the OAE 2
at Site 1258 and 3.4% (ST cf 6.5%) within the OAE 2 at Site 1260.
3.3. Iron
Figs. 3 and 4 show profiles of total iron and Al-normalized iron
contents. Only for some carbonate-rich layers Fe contents are below the
quantification limit of 0.33% (e.g. ~424 mcd at Site 1260) and FeT/Al
peaks may be exaggerated (see Section 3.1.) due to inaccuracies of
measurements of Fe and Al close to or below the quantification limit.
Besides these peaks, the FeT/Al profiles show an almost constant value
close to AS. Assuming severe oxygen-deficiency, as evidenced by
sediment lamination for the black shale sequence of Demerara Rise,
the almost constant average shale-like values of FeT/Al imply anoxic but
not euxinic (no free H2S in the water column) conditions during
deposition. FeT/Al ratio of the sediment is neither decreased via
mobilization of iron(hydr)oxides under suboxic conditions nor
increased via precipitation of dissolved Fe species as sulfide in the
overlying water column under euxinic conditions. During OAE 2 FeT/Al
mean values increase to 0.76 (Site 1258, maximum 1.72) and 0.80 (Site
1260, maximum 1.89), owing to an increase in total FeT contents. This
indicates an additional Fe-source during deposition of this interval. In
analogy to the modern Black Sea reductive Fe mobilization in near-shore
areas or enhanced fluvial input are likely causes for the observed Fe-
enrichment (e.g., Lyons and Severmann, 2006). In the case of the modern
Black Sea FeT/Al-ratios are increasing with water depth (e.g. Wijsman
et al., 2001) because syngenetic iron sulfides form an increasing part of
bulk sedimentary iron. This model requires truly euxinic conditions,
besides the existence of a zone where reducing but non-sulfidic
conditions prevail, allowing Fe transport from shallow to deep sites
(e.g., Lyons and Severmann, 2006). The increase of the ratio of pyrite iron
to total iron, FeP/FeT, from a mean value of 0.44 below and above to about
0.64 (Table 4) within OAE 2 indicates the addition of syngenetic water
column-derived pyrite (Raiswell and Canfield, 1998; Poulton and
Raiswell, 2002; Böttcher et al., 2006, and references therein). Together
with previous measurements on the detailed reactive iron speciation of
Leg 207 sediments (Böttcher et al., 2006), these findings are confirmed
by the Al-normalized iron contents, as discussed above. Fig. 5 presents
the analytical data of Sites 1258 and 1260 in a ternary Fex–ST–TOC plot
(Brumsack, 1988; Dean and Arthur, 1989; Brumsack et al., 1995). The
represented data within the OAE all plot below the pyrite-saturation line
indicating, that under iron-limited conditions, some (excess) sulfide
and/or sulfur intermediates were able to react with organic matter to
form organic sulfur compounds.
3.4. Sulfur and sulfur isotopes
Dissimilatory sulfate reduction leads to the formation of hydrogen
sulfide that may transform reactive iron to iron sulfides (essentially
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328 pp. 307–308

Fig. 3. Depth-profiles for TOC, TIC, Al, ST, SORG, SP, SAVS and FeT for Cenomanian/Turonian black shales at Site 1258. TOCcf and ST cf are calculated for carbonate-free sediment. δ34S of
pyrite, FeT/Al ratios as well as FeP/FeT ratios are also shown. Grey: OAE 2; grey solid line: element/Al ratio of to ‘average shale’ (AS) (Wedepohl, 1971, 1991); dashed line: quantification
limit (see Appendix A).
pp. 309–310 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

Fig. 4. Depth-profiles for TOC, TIC, Al, ST, SORG, SP and FeT for Cenomanian/Turonian black shales at Site 1260. TOCcf and ST cf are calculated for carbonate-free sediment. FeT/Al ratios as
well as FeP/FeT ratios are also shown. Grey: OAE 2; grey solid line: element/Al ratio of ‘average shale’ (AS) (Wedepohl, 1971, 1991); dashed line: quantification limit (see Appendix A).
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328 311

Table 3
Comparison of average element contents and element/Al ratios Cenomanian/Turonian black shales of Demerara Rise and ‘average shale’

1258 below OAE 2 1258 within OAE 2 1258 above OAE 2 1260 below OAE 2 1260 within OAE 2 1260 above OAE 2 Average shale
(n = 347) (n = 197) (n = 274) (n = 129) (n = 26) (n = 57) (Wedepohl, 1971, 1991)
ST % 1.71 4.97 2.35 1.45 3.43 1.69 0.24
TIC % 6.20 2.46 5.00 7.59 5.76 6.34 0.35
TOC % 7.83 17.82 10.13 6.89 12.12 7.54
Si % 11.61 14.66 11.43 6.64 8.06 9.14 27.53
Ti % 0.08 0.14 0.12 0.08 0.10 0.10 0.46
Al % 1.68 2.90 2.57 1.47 2.17 2.18 8.84
FeT % 0.88 2.17 1.19 0.76 1.65 0.97 4.80
Mg % 0.47 0.46 0.57 0.47 0.47 0.60 1.60
Ca % 21.37 9.44 18.27 26.04 20.20 22.32 1.57
Na % 0.68 1.16 0.99 0.74 0.86 0.82 1.19
K % 0.45 0.89 0.74 0.43 0.65 0.69 2.99
P % 0.25 0.15 0.54 0.29 0.22 0.52 0.07
As ppm 13 25 21 18 25 16 10
Ba ppm 260 542 612 343 746 642 580
Co ppm 3 13 5 3 9 4 19
Cr ppm 121 70 149 109 82 145 90
Cu ppm 58 68 70 53 68 63 45
Mn ppm 7 50 27 0 14 7 850
Mo ppm 80 40 95 62 33 38 1
Ni ppm 126 169 149 108 144 92 68
Rb ppm 21 30 30 19 22 26 140
Sr ppm 593 653 716 923 952 792 300
U ppm 12 17 18 16 18 12 4
V ppm 1058 370 1173 1386 554 899 130
Y ppm 12 29 23 13 23 19 41
Zn ppm 578 138 968 879 382 701 95
Zr ppm 28 38 36 27 33 34 160
ST cf % 3.83 6.26 4.36 4.04 6.47 4.70 0.25
TOCcf % 17.64 22.40 18.30 18.74 22.80 19.30
ST/Al 1.05 1.75 1.05 1.06 1.67 1.54 0.03
TOC/Al 4.85 6.32 4.40 4.94 5.93 5.98
Si/Al 7.79 5.81 4.76 4.49 3.72 4.24 3.11
Ti/Al 0.05 0.05 0.05 0.05 0.05 0.05 0.05
FeT/Al 0.55 0.76 0.50 0.58 0.80 0.74 0.54
Mg/Al 0.57 0.17 0.25 0.55 0.25 1.39 0.18
Ca/Al 42.97 4.36 11.69 43.01 13.87 121.32 0.18
Na/Al 0.43 0.41 0.42 0.57 0.42 0.58 0.13
K/Al 0.28 0.31 0.29 0.32 0.31 0.40 0.34
P/Al 0.13 0.05 0.20 0.17 0.12 0.23 0.01
As/Al ×10− 4 9.3 8.8 8.4 14.3 12.5 13.6 1.1
Ba/Al ×10− 4 190.8 188.1 239.0 271.8 345.2 531.6 65.6
Co/Al ×10− 4 2.1 4.4 2.3 2.2 4.4 3.2 2.1
Cr/Al ×10− 4 68.8 24.0 50.7 75.1 37.5 57.7 10.2
Cu/Al ×10− 4 36.0 24.0 27.4 38.9 30.5 45.9 5.1
Mn/Al ×10− 4 9.2 18.4 23.2 0.1 5.9 36.2 96.2
Mo/Al ×10− 4 50.0 14.3 40.4 49.4 16.7 20.3 0.1
Ni/Al ×10− 4 77.8 59.5 62.0 85.0 73.0 47.6 7.7
Rb/Al ×10−4 11.5 10.2 11.3 12.1 10.7 10.6 15.8
Sr/Al ×10−4 584.4 241.5 349.0 1019.4 541.5 1425.7 33.9
U/Al ×10− 4 9.7 6.2 8.5 14.5 10.8 17.9 0.4
V/Al ×10− 4 654.8 127.0 461.7 1010.1 294.5 439.8 14.7
Y/Al ×10− 4 8.9 10.1 10.2 10.6 13.1 17.0 4.6
Zn/Al ×10− 4 316.0 48.1 355.9 581.4 154.0 251.1 10.7
Zr/Al ×10− 4 20.7 13.5 14.9 22.4 17.1 31.8 18.1

Italics: average values below quantification limit (see Appendix A).

pyrite, FeS2; including framboidal pyrite Fig. 6) and, under iron limited during OAE 2 at both sites (Figs. 3 and 4; see also Table 4). Below OAE 2 SP
conditions with organic matter to form organic sulfur compounds (e.g. values are ~0.4% (ca. 25 rel% of ST) and SORG ~1.2% (respectively ca. 75 rel%
Werne et al., 2004). The profiles of SP and SORG show elevated values of ST). At Site 1258, SP contents rise to ~1.7% (maximum N2.5%) and SORG
to ~4.4% (maximum N7.7%) within the OAE 2 interval, thus the proportion
Table 4 of pyrite sulfur increases to ca. 28 rel% of total sulfur. Although absolute
Average pyrite sulfur (SP), pyrite iron (FeP), acid volatile sulphur (SAVS), calculated
organic sulfur (Sorg) and ratio of pyrite (reactive) iron to total iron (see Table 3)
values are not as high as at Site 1258, the pyrite sulfur fraction at Site 1260
reaches even ca. 33 rel% with 1.1% SP (maximum N3.1%) and 2.3% SORG
1258 1258 1258 1260 1260 1260 (maximum N6.6%) during OAE 2. Above OAE 2 the proportional
below within above below within above
composition of different sulfur species nearly equals the composition
OAE 2 OAE 2 OAE 2 OAE 2 OAE 2 OAE 2
(n = 19) (n = 18) (n = 12) (n = 16) (n = 22) (n = 13) below with ~0.5% SP and ~1.4% SORG (SP:SORG =26:74 rel%) at both sites.
SP % 0.42 1.68 0.60 0.38 1.14 0.52 The relationship of SP with TOC data is presented in Fig. 7a and compared
FeP % 0.36 1.46 0.52 0.33 0.99 0.45 to the relationship proposed for “normal marine sediments” (Berner and
SAVS ppm 22.4 (n=17) 0.5 (n=13) 12.2 (n=11) Raiswell, 1983). Only a few data points coincide with the relation found
Sorg % 1.25 4.39 1.69 1.14 2.31 1.41 for clastic sediments below an oxic water column (dashed line in Fig. 7a).
FeP/FeT 0.41 0.67 0.44 0.43 0.60 0.46
A number of data points plot above the regression line, indicating an
312 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328
Fig. 5. Ternary plot: degree of pyritization of Cenomanian/Turonian black shales at Demerara Rise in the Fex–TOC–ST · 2 system (relative weight ratios). Reactive Fex is calculated with
Fex = FeT − 0.25 · Al. Data point for pyrite is also shown.
excess of sulfur that may be due to euxinic depositional conditions. At
highest TOC contents, however, most data show a relative excess of
organic matter (OM). The indicated iron-limitation during black shale
deposition has also been found for the modern Black Sea sapropel and
Mediterranean sapropels (e.g. Lyons and Berner, 1992; Passier et al.,
1999b; Böttcher et al., 2006). SP in the investigated black shale samples
makes up between 30% and 100% of ST, with a decrease of the relative
amount of SP with increasing OM content. This indicates the importance
of the balance between organic matter and the syngenetic metal flux to
the surface sediments in controlling the sedimentary sulfur speciation. In
addition to fixation of sulfide by the reaction with iron, organic matter
acted as the second important sulfur trap during early diagenesis. From
molecular analysis of the preservation pathways of sedimentary organic
carbon in a euxinic environment Hebting et al. (2006) proposed that
sulfides produced by bacterial sulfate reduction play a major role for the
reductive alteration and thus preservation of organic carbon. From the
nearly linear variation of organic sulfur and organic carbon contents
(Fig. 7b), essentially constant atomic SORG/TOC ratios are obtained.
Quantitatively, the samples with TOC contents exceeding ~2 wt.% have as
much as 10 atom% organic sulfur. Most of the atomic S/C ratios fall in the
range of 0.04 to 0.06, which is within the range reported for sapropels
from the Mediterranean and Black Sea (Passier et al., 1999b; Böttcher
et al., 2006). The almost linear relationship between TOC and SORG may be
caused by a constant relative proportion of organic matter fractions
available for diagenetic sulfurization.
The downcore variation of the stable sulfur isotope composition of
pyrite at Site 1258 displays a range in δ34S values between −28.2 and
+0.2‰ (average −15.4 ± 8.3‰; n= 41) during OAE 2, with an inverse
relationship to the δ13C values (Fig. 3, Table 5). The sulfur isotope
variations observed in the sedimentary pyrite pool are much more
pronounced than those observed in the global seawater sulfate at this
time (Paytan et al., 2004). This indicates that sulfur isotope discrimi-
nation was controlled by changes in sedimentary conditions and was
higher during times of enhanced burial of OM. This can be caused by a
lower burial efficiency of reduced sulfur and/or higher contributions
from the oxidative part of the sulfur cycle (in the water column or in
surface sediments). A similar trend and magnitude of sulfur isotope
discrimination was found in the C/T sediments of different sites in the
Tarfaya basin (e.g. Kolonic et al., 2002; Böttcher et al., unpublished data).
For instance for the pyrite fraction Böttcher et al. (unpublished data)
obtained ranges at Site S13 (−18.9 to +2.5‰, average −10.2 ±7.8‰; n =9),
at S57 (−28.8 to −8.8‰, average −17.6 ±5.1‰; n =29), and S75 (−20.6 to
−8.7‰, average −15.7± 3.2‰; n =17). This similarity suggests a common
control of the overall sedimentary sulfur isotope signal for the CTBE in the
southern North Atlantic independent of paleo-water depths. The
stratigraphic trend of the sulfur isotope ratios shows that pyrite isotope
data go through a minimum similar to previous observations at Tarfaya
(Kolonic et al., 2002; Böttcher et al., unpublished data). We relate the
most negative values to an increased contribution of syngenetic pyrite,
sulfur derived from the oxidative part of the biogeochemical sulfur cycle,
and mostly changes in other factors (e.g., the quality of organic matter)
influencing overall sulfur isotope discrimination. Most lighter sulfur
isotope data are found during OAE 2 compared to sediments outside OAE
2 (Fig. 8), and these are associated with highest contents of pyrite-iron.
This is in agreement with findings of Gauthier (1987) on Cretaceous black
shales from the Western Interior Seaway. Taking the sulfur isotopic
composition for seawater sulfate during the Cenomanian/Turonian to be
around +15‰ (Strauss, 1999; Paytan et al., 2004), and assuming that
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328
Fig. 6. EDX-Scan and SEM of a pyrite framboid from Site 1258B-45-4 138–139 cm, 422.98 mcd (within OAE 2).
pyrite mainly formed under conditions that were open with respect
to dissolved sulfate (Hartmann and Nielsen, 1969), e.g., in the water
column or close to the sediment–water interface, an overall sulfur
isotope fractionation of 15 to 42‰ is estimated for Site 1258. This is
within the range found in studies with pure cultures of sulfate-reducing
bacteria (e.g. Brunner and Bernasconi, 2005), but is smaller than values
found in C/T sediments from the northern North Atlantic (Böttcher and
Kuypers, unpublished data), in the Pliocene TOC-rich sapropels of the
deep Mediterranean (Passier et al., 1999a; Böttcher et al., 2003), in the
modern euxinic Black Sea (Neretin et al., 2004; Böttcher et al., 2004), and
in sediments from the Great Australian Bight (Wortmann et al., 2001).
Higher contributions from the oxidative part of the sulfur cycle (microbial
disproportionation of sulfur intermediates) and/or lower cellular sulfate
reduction rates or specific bacterial communities may be responsible for
the development of the different characteristic sulfur isotope signals.
3.5. Redox-sensitive and sulfide forming trace metals
3.5.1. Manganese
The C/T black shales of Demerara Rise are characterized by very low
Mn-concentrations (Fig. 9). For most of the samples the Mn contents are
below the XRF quantification limit of 78 ppm. At Site 1258, for sediments
below 427.7 mcd Mn values are below the detection limit, which is
defined as half the quantification limit. Right below, within and above
OAE 2, Mn contents are higher and reach the detection limit of 39 ppm.
Within OAE 2, Mn values show a high variability between detection limit
313
and 426 ppm, with a mean value of ~50 ppm and a standard deviation of
the same order (49 ppm). Above OAE 2 (421.63–421.03 mcd) a clear peak
in absolute Mn concentrations with a maximum value of 217 ppm can be
recognized. This peak can be correlated to a peak in TIC. Since Mn
concentrations often are below the quantification limit, Mn/Al ratios
have to be considered with caution. A maximum Mn/Al ratio of 466× 10− 4
at 421.63–421.03 mcd represents a significant Mn enrichment in
comparison to the Mn/Al ratio of 96 ×10− 4 for average shale (Wedepohl,
1971, 1991). The same is true for certain intervals within OAE 2. For
samples close to the onset and termination of OAE 2, the enrichments in
Mn are less pronounced.
At Site 1260 Mn concentrations in all samples are below the
quantification limit. Only a few samples attain the detection limit of
39 ppm: One interval above OAE 2 (423.99–424.04 mcd) reaching Mn
values up to 77 ppm can again be correlated to a carbonate peak.
Within OAE 2 Mn concentrations vary between 0 and 46 ppm.
Extremely low Mn/Al ratios in C/T black shales of Demerara Rise
indicate that Mn was either reduced within the water column before
sedimentation or upon early diagenesis in an environment open to
dissolved Mn(II) loss as provided by an expanded oxygen-minimum-
zone (OMZ), like the modern upwelling zones off Peru (Böning et al.,
2004) or in the Gulf of California (Brumsack, 1989). Thurow et al.
(1992) found a similar mobilization of Mn at the Northwest Australian
margin during OAE 2. The authors described Mn-poor sediments
within the OMZ and Mn-rich sediments below the OMZ, indicating
oxic deep waters during the C/T interval at this location.
314 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

Fig. 8. δ34S of pyrite versus pyrite iron (FeP) for Cenomanian/Turonian black shales at
Site 1258.

ponsible for Mn enrichment in Black Sea sediments. Pre-existing carbo-

nates may act as an efficient trap for diagenetically mobilized Mn(II)
(Boyle, 1983; Gingele and Kasten, 1994; Böttcher, 1997).
At Demerara Rise elevated Mn/Al ratios are only seen in distinct
horizons with high carbonate contents below (Site 1258) and above OAE
2 (Site 1258 and Site 1260). We therefore relate these Mn/Al peaks in C/T
black shales to carbonate diagenesis. There is no correlation to FeT/Al
ratios that would point to simultaneous mobilization from suboxic
sediments and precipitation under sulfidic conditions as described by
Lyons and Severmann (2006).
The higher Mn contents at Site 1258 might originate from the
position in greater paleo-water depths. Assuming the existence of an
OMZ, Site 1258 might be located below the OMZ where during times
of weaker anoxia, Mn(IV)-bearing phases reached the sediment and
later were transformed into mixed Ca–Mn-carbonates.
Within OAE 2, Mn values show a high variability as described
above. As all OAE 2 samples with higher Mn/Al ratios are located near
the presumed “ash-layers”, the import of Mn(IV)-bearing phases could
also be attributed to the different detritus composition (average Mn
contents: 332 ppm compared to 17 ppm mean value for all C/T black
shales of this study, see Appendix B-c). If Mn was released to the pore
space after burial, Mn concentrations in the pore water within these
“ash-layers” and adjacent intervals might have been higher. Because
TIC contents are not elevated (1.7–8.1%, mean value 5.6%), precipita-
tion of Mn-carbonate is questionable in these intervals.
Besides increased availability of dissolved Mn, pore volume may
Fig. 7. (a) Pyrite sulfur (SP) versus TOC and (b) organic sulfur (SORG) versus TOC for
influence the potential for precipitation of Mn-bearing minerals during
Cenomanian/Turonian black shales at Site 1258 and Site 1260 (this study) and black shale
samples from Sites 1257, 1259 and 1261 (Böttcher et al., 2006). Dashed line marks the
diagenesis. The carbonate-rich layers with elevated Mn contents are
relationship derived for normal marine sediments as defined by Berner and Raiswell (1983). visually affected by carbonate diagenesis, e.g. precipitation of calcite
(Erbacher et al., 2004). Increased pore volume, either through the
A possibility for the observed Mn-enrichment might be the fixation occurrence of foraminiferal packstones or of “ash-like” layers, may
of dissolved Mn(II) as mixed Mn–Ca-carbonates under conditions where have favored authigenic formation of Mn-bearing minerals.
Mn was enriched. Brumsack (2006) suggests that overgrowths of early
diagenetic Mn-carbonate on pre-existing carbonate tests might be res- 3.5.2. Cobalt
Under oxygen depleted conditions like in an OMZ, Mn–and Fe-oxi/
hydroxide-associated Co would be mobilized and transported away. In
Table 5
Average δ34S of pyrite sulfur (SP) for Cenomanian/Turonian black shales of Site 1258 Gulf of California upwelling sediments (Brumsack, 1989) or the Peruvian
margin (Böning et al., 2004), Co is depleted similar to Mn. In contrast to
1258 below OAE 2 1258 within OAE 2 1258 above OAE 2
Mn, which forms stable sulfides only under very special conditions, Co
(n=16) (n=12) (n=13)
precipitates as CoS when free hydrogen sulfide is present (Heggie and
δ34SP ‰ −8.4 −24.4 −15.6
Lewis, 1984; Gendron et al., 1986).
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328 315

Fig. 9. Depth-profiles for Mn, Mn/Al, Co and Co/Al for Cenomanian/Turonian black shales at Site 1258 and Site 1260. Grey: OAE 2; grey solid line: element/Al ratio of ‘average shale’
(AS) (Wedepohl, 1971, 1991); dashed line: quantification limit (see Appendix A).

The profiles of Co concentration (Fig. 9) at Site 1258 and Site 1260
show that nearly all sediments below and above OAE 2 are characterized
by very low Co concentrations (often below the quantification limit of
9 ppm). Co/Al ratios for Demerara Rise C/T black shales below and above
OAE 2 are similar to the Co/Al ratio of average shale (2.1 × 10− 4;
Wedepohl, 1971, 1991). Within OAE 2, Co/Al ratios increase to a mean
value of 4.4 × 10− 4 at both sites with maximum values of 9.4 × 10− 4 at Site
1258 and 10.3 × 10− 4 at Site 1260.
Thus, the Co distribution is quite similar to the Fe distribution: Under
reducing conditions the constant average shale-like value of Co/Al rather
indicates fixation of dissolved Co as sulfide than preservation of parti-
culate Co-bearing (hydr)oxide phases. As the Co increase during OAE 2
requires an additional Co-source during deposition, we assume a trans-
port mechanism analogous to Fe from near-shore areas, where reducing
but non-sulfidic conditions mobilize additional Co, which is then fixed
under truly euxinic conditions further offshore.
3.5.3. Zinc
Cretaceous black shales are known to be highly enriched in Zn.
Brumsack (2006) gives a Zn/Al ratio 459 × 10− 4 as a C/T mean value
(AS = 10.7 ×10− 4; Wedepohl, 1971, 1991). Hetzel et al. (2006), found
370 ×10− 4 as a mean value of the Cretaceous black shales of Demerara
Rise (all sites). The high-resolution study of the C/T interval presented
here reveals considerable variability in Zn/Al ratios (Fig. 10). The depth
316 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328
profile of Site 1258 shows Zn/Al ratios in the same order of magnitude as
described by Hetzel et al. (2006) below and above OAE 2 (mean values of
316.0 × 10− 4 and 355.9 ×10− 4, respectively; see Table 3). The maxima
below and above OAE 2 correspond to maxima in the SAVS profile, indi-
cating the presence of metal sulfides other than pyrite. At Site 1260, the
Zn/Al ratios are slightly higher below OAE 2 (mean value 581.4 ×10− 4),
while above OAE 2 ratios are lower (mean value 251.1 × 10− 4). At both sites
a distinct decrease in Zn/Al ratios during OAE 2 can be observed (mean
values 48.1 × 10− 4 at Site 1258 and 154.0 ×10− 4 at Site 1260).
Addressing the distribution patterns of Co and Zn discussed above
we found two different enrichments patterns for these trace metals,
both known to be enriched in C/T black shales (Brumsack, 2006) by
forming stable sulfides. Whereas C/T black shales from Demerara Rise
are enriched in Co during OAE 2, but not before and thereafter, the
enrichment in Zn is present throughout the studied interval and
displays a rapid decrease in the degree of enrichment within OAE 2.
3.5.4. Molybdenum and vanadium
Overall, element/Al ratios of both Mo and V show clear enrichments
in C/T black shales of Demerara Rise (mean Mo/Al = 28.2 × 10− 4,
AS = 0.15 × 10− 4, mean V/Al = 443.8 × 10− 4, AS = 14.7 × 10− 4; Wedepohl,
1971, 1991; Fig. 10). Mo and V are relatively unreactive in oxic seawater,
but are known to be concentrated in sediments overlain by anoxic
waters (Brumsack and Gieskes, 1983; Brumsack, 1986).
Vanadium in oxic seawater should be present as V(V). Under
moderately reducing conditions, V(IV) forms vanadyl ions (VO2−) that
may be removed to the sediment by surface adsorption processes or
by formation of organometallic ligands (Emerson and Huested, 1991;
Morford and Emerson, 1999). Under more reducing conditions, the
presence of free H2S released by bacterial sulfate reduction causes V to
be further reduced to V(III), which can be taken up by geoporphyrins
or be precipitated as the solid oxide V2O3 or hydroxide V(OH)3 phase
(Breit and Wanty, 1991; Wanty and Goldhaber, 1992).
The stable oxidation state of Mo in oxic seawater is Mo(VI). Reduction
of Mo(VI) to Mo(IV) and authigenic enrichment in sediments occur under
euxinic conditions (Crusius et al., 1996) possibly via diffusion across the
sediment–water interface (Emerson and Huested, 1991). Helz et al.
(1996) suggested a threshold concentration for H2S, above which Mo is
transformed to particle-reactive thiomolybdates that are scavenged by
forming bonds with metal-rich particles, sulfur-rich OM and pyrite.
Tribovillard et al. (2006) addressed the reconstruction of the redox
environment of sediments overlain by oxygen-depleted waters via the
combined use of different trace metals. While V is reduced and can
accumulate under denitrifying conditions, Zn and Mo are enriched
mainly under sulfate-reducing conditions. Thus, in the case of V
enrichment without Mo enrichment, the authors postulate suboxic/
anoxic depositional conditions without free H2S, whereas sediments
exhibiting concurrent enrichments in V and Mo reflect euxinic
conditions at the sediment–water interface or in the water column
(Algeo and Maynard, 2004; Tribovillard et al., 2004). As the C/T black
shales of Demerara Rise are clearly enriched in both, Mo and V, this
simplified distinctive feature would hint to euxinic conditions for the
depositional environment.
From positive correlations of Mo with sulfurized OM in ancient
marine black shales, Tribovillard et al. (2004) emphasized Mo trapping
by sulfur-rich OM. No correlation of Mo with pyrite accumulation could
be found. Instead, the reduced availability of reactive Fe may favor Mo
accumulation, as significant OM sulfurization is only possible when
reactive iron is limited. As shown above, we find iron-limitation in
most of the studied intervals and an enhanced OM sulfurization during
OAE 2. Following the arguments of Tribovillard et al. (2004), we would
expect an increase in Mo enrichment during OAE 2. Instead, a clear
decrease is visible, implying that other factors influenced Mo
accumulation as well. Probably, the concentration of dissolved sulfide
in the water column that affected aqueous Mo speciation may have
influenced the efficiency of Mo fixation (Neubert et al., in press).
For anoxic basins, Emerson and Huested (1991) showed that the
concentrations of Mo and V in the water column are usually lower than
in oxic seawater due to their uptake into highly anoxic sediments. As no
systematic relationship between the deep-water Mo or V concentrations
and H2S content was found, the authors concluded that concentrations
of Mo and V are rather controlled by their flux to sediments and water
renewal from outside the basins than by changes in water column
anoxia. Algeo and Lyons (2006) analyzed Mo–TOC relationships in
sediments from anoxic environments characterized by different degrees
of hydrographic restriction. In silled anoxic basins, decreasing Mo/TOC
ratios with increasing degree of restriction imply that sedimentary Mo
concentrations were controlled by Mo availability from the overlying
water column, and thus by resupply of Mo via deepwater renewal. Algeo
and Lyons (2006) termed this drawdown of Mo concentrations in deep
water during stagnant intervals the “basin reservoir effect”.
Fig. 11 shows Mo/TOC profiles as well as X–Y-plots of Mo versus TOC.
Mo/TOC values vary between ~5 × 10− 4 and ~20× 10− 4 for sediments
deposited before OAE 2. Similar to Mo/Al, Mo/TOC ratios decrease rapidly
at the onset of OAE 2, staying low during OAE 2, before a slight increase is
visible after OAE 2. The slopes of regression lines for X–Y-plots of Mo
versus TOC give similar low Mo/TOC ratios for samples within the OAE 2
interval at both sites (2.3× 10− 4 at Site 1258 and 2.4× 10− 4 at Site 1260).
These values are even lower than the value of Mo/TOC= 4.5 ± 1 × 10− 4
reported by Algeo and Lyons (2006) for the Black Sea. Regression lines for
samples deposited before OAE 2 give Mo/TOC values of 10.7× 10− 4 at Site
1258 and 8.8× 10− 4 at Site 1260. The increase in Mo/TOC ratios after OAE
2 is less pronounced at Site 1260 (Mo/TOC = 5.2× 10− 4) than at Site 1258
(Mo/TOC = 9.4 × 10− 4).
As V burial under anoxic conditions is also known to be linked to OM
(Breit and Wanty, 1991; Emerson and Huested, 1991; Morford and
Emerson, 1999), we analyzed V/TOC ratios analogues to Mo and Zn/ST
ratios as Zn is known to form stable sulfides if H2S is present (Jacobs et al.,
1985) (Fig. 11). Both, V and Zn, show the distinct decrease relative to TOC
and ST during OAE 2 pointing to decoupling of OM burial, sulfidization
and TM availability during OAE 2.
Fig.12 shows the enrichment factors relative to average shales for FeT,
Co, Mo, V and Zn for Sites 1258 and 1260, and for C/T mean values
(Brumsack, 2006). The enrichment factor for FeT is ~1 at Site 1258 below
and above the CTBE and at Site 1260 below the CTBE, indicating Fe/Al
ratios similar to average shale. The observed enrichment in sediments of
Site 1260 above the CTBE may be an artefact owing to normalization of
values close to the Fe and Al detection limit in carbonate-rich sediments
(see Fig. 4, ~424 mcd). As described above, the distribution patterns of Co
are similar to those of FeT.
Zn, Mo and V show similar enrichment patterns, with highest values
below, intermediate values above, and lowest values within OAE 2. At
Site 1258, Mo, V and Zn are enriched to similar degrees below and above
OAE 2. The decline of enrichment during OAE 2 is more pronounced than
for Site 1260. Overall, the degrees of enrichment of Mo, V and Zn are
similar to other C/T sediments listed by Brumsack (2006). Only the
sediments deposited during OAE 2 at Site 1258 are characterized by less
pronounced Mo, V and Zn enrichments relative to other C/T black shales.
In summary, we suggest two important mechanisms affecting FeT and
trace metal distribution patterns in C/T black shales at Demerara Rise:
Locally, Mn depletion hints to reducing conditions an open-marine
environment, e.g. an OMZ. FeT and Co enrichments during OAE 2 indicate
an expansion of this OMZ. As their seawater concentrations are generally
low, at least part of the sedimentary FeT and Co enrichments during OAE 2
must be due to mobilization from oxygen-depleted nearshore-sediments.
Whereas Fe and Co are conveyed along with Mn in suboxic waters, they
will be precipitated as sulfides when hydrogen sulfide is present in the
water column.
Regarding the source for TMs enriched in TOC-rich sediments, Mo
and V are highly concentrated in seawater, and they may have become
enriched in the sediment via diffusion from the water column. As
extreme Zn enrichments in Cretaceous black shales (compared to
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328 pp. 317–318

Fig. 10. Depth-profiles for Mo, Mo/Al, V, V/Al, Zn and Zn/Al for Cenomanian/Turonian black shales of Site 1258 and Site 1260. Grey: OAE 2; grey solid line: element/Al ratio of ‘average
shale’ (AS) (Wedepohl, 1971, 1991); dashed line: quantification limit (see Appendix A).
pp. 319–320 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

Fig. 11. (a) Depth-profiles for Mo/TOC, V/TOC and Zn/ST for Cenomanian/Turonian black shales at Site 1258 and Site 1260. Grey: OAE 2. (b) X–Y-Plots for Mo versus TOC, V versus TOC
and Zn versus ST. Slopes of regression lines (solid for Site 1258, dashed line for Site 1260) are given in units of 10− 4.
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328 321

Fig. 12. Mean enrichment factors (EF) of FeT, Co, Mo, V and Zn relative to ‘average shale’ (AS) (Wedepohl, 1971, 1991) for Cenomanian/Turonian black shales at Demerara Rise.
EF = element/Al(sample)/element/Al(AS). (a) Site 1258, (b) Site 1260. Dashed lines: EF for C/T mean values (Brumsack, 2006).

recent TOC-rich sediments) require an additional Zn source, a higher
seawater concentration of Zn due to hydrothermal input during the
Cretaceous seems likely (Arthur et al., 1988; Brumsack, 2006). Under
such conditions seawater might again be the dominating source for Zn
enrichments. Thus, on a larger if not global scale, we emphasize a
decline in seawater TM availability during OAE 2, revealed by the
decrease in Mo, V and Zn enrichment.
Taking seawater as the dominant source for Mo, V and Zn, the
depletion in TM/Al may reflect the global onset of black shale
deposition during OAE 2 and the rapid drawdown of the seawater
TM reservoir by the spreading of euxinic depositional areas. In the
modern oceans, only 0.2% of the seafloor are hypoxic (Helly and Levin,
2004), while during the Cretaceous, particularly during OAE 2, such
conditions were much more wide-spread. Kuypers et al. (2002)
pointed out that the proto-North Atlantic Ocean was one of the main
sites of carbon burial during OAE 2. Paleogeographic reconstructions
show that the proto-North Atlantic Ocean was a restricted area with
major seawater supply coming from the Tethys only. The black shales
deposited in the Tethys and in the proto-North Atlantic Ocean during
OAE 2 (e.g. Kuhnt et al., 1990) definitely formed a significant TM sink.
We therefore assume that the decline in TM enrichment seen at
Demerara Rise indicates a drawdown of TMs from seawater, similar to
the “basin reservoir effect” described by Algeo and Lyons (2006).
3.6. Productivity proxies
Fig. 13 show the enrichments factors for some elements, used for
approximation of paleoproductivity.
Phosphorus belongs to the essential nutrient elements controlling
marine primary productivity (e.g. Broecker and Peng, 1982). High
concentrations are found in recent upwelling sediments pointing
towards enhanced nutrient supply and resulting high bioproductivity
(e.g., Böning et al., 2004). Incorporated into organic material (e.g. in
marine phytoplankton; Redfield, 1958) P is deposited in the sediment,
where it is preferentially remineralized relative to TOC and liberated to
the pore water and maybe forming authigenic phosphatic precipitates.
Under oxygen-depleted conditions, when potential phosphate scaven-
gers such as Fe-(hydr)oxides are reduced and not available, organic P
release in sediments is even higher. Therefore, in TOC-rich sediments
deposited under anoxic conditions the TOC/P ratio should be increased
(Ingall et al., 1993 and references therein).
Nederbragt et al. (2004) concluded from measurements of total
phosphorus and organic carbon in C/T sediments from the Tarfaya Basin,
Morocco, that the main underlying mechanism that allowed and
sustained enhanced carbon burial during the mid-Cretaceous was a
perturbation of the oceanic phosphorus cycle. More effective regeneration
of organic phosphorus under anoxic conditions can lead to an increase in
322 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

dissolved oceanic phosphate, which in turn stimulates surface-water
productivity (Ingall et al., 1993; Bjerrum and Canfield, 2002; Mort et al.,
2007). The Shipboard Scientific Party (2004) describes the presence of P-
rich concretions in black shales of Demerara Rise. Fig. 13 shows a clear
enrichment of P relative to average shale in the sections studied. This
points towards a high primary productivity comparable to coastal
upwelling areas. The minor enrichment during OAE 2 hints to a decreasing
nutrient supply or to partial loss of P during at least periodically truly
anoxic conditions in comparison to the situation before and thereafter.
The non-lithologenic excess barium has been interpreted as a
paleoproxy for bio-productivity (Schmitz, 1987; Dymond et al., 1992;
Paytan et al., 1996). These biogenic barites (BaSO4) (Bishop, 1988;
Bertram and Cowen, 1997; Paytan et al., 2002; Bernstein and Byrne,
2004) are only stable under seawater sulfate concentrations (Church and
Wohlgemuth, 1972). Due to the microbial sulfate reduction in TOC-rich
sediments, barite may be dissolving, leading to the mobilization of Ba
(Brumsack and Gieskes, 1983; McManus et al., 1998; Eagle et al., 2003).
Authigenic barite may precipitate at the top of the sulfate-depletion
zone forming diagenetic barite fronts within or above TOC-rich strata
(Torres et al., 1996; Bréhéret and Brumsack, 2000).
Hetzel et al. (2006) found the highest Ba/Al above the Cretaceous black
shales, while within the black shales Ba/Al ratios are still high despite of
the present absence of sulfate in the pore waters (Erbacher et al., 2004).
Arndt et al. (2006) showed in a transport-reaction model that not only OM
degradation but also anaerobic oxidation of methane (AOM) above the
black shales of Demerara Rise influences sulfate availability and therefore
the remobilization of biogenic barium. These authors further showed that
temporal dynamics of degradation processes caused various shifts of the
barite precipitation zone during burial, thus inhibiting the formation of an
authigenic barite front or causing the dissolution of earlier formed fronts.
Fig. 13 shows an enrichment of Ba similar to the C/T mean values
from Brumsack (2006). This enrichment indicates elevated primary
productivity during deposition. But a large fraction of former barite
may have been remobilized and formed diagenetic barites above the
black shales. For this reason the use of Ba as a paleoproxy on a
quantitative level (Dymond et al., 1992) for Cretaceous settings in such
an environment is highly questionable.
4. Paleoenvironmental implications and comparison with
other paleoproxies
The paleoconditions for the depositional environment based on
geochemical arguments are summarized in Fig. 14. From analysis of
TOC–Fe–S systematics and TM distribution patterns we can conclude
that a depositional environment with an expanded oxygen-minimum-
zone (OMZ) similar to coastal upwelling areas existed before the onset of
OAE 2 (Fig. 14a). Enrichments of TOC, P and Ba hint to enhanced
bioproductivity. The depletion in Mn and enrichment in redox-sensitive

Fig. 13. Mean enrichment factors (EF) of Si, P and Ba relative to ‘average shale’ (AS) (Wedepohl, 1971, 1991) for Cenomanian/Turonian black shales at Demerara Rise. EF = element/Al
(sample)/element/Al(AS). (a) Site 1258, (b) Site 1260. Dashed lines: EF for C/T mean values (Brumsack, 2006).
 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328
TM indicate at least suboxic conditions. During OAE 2, an increase in the
FeP/FeT ratio points to the rapid development of truly euxinic conditions
with free hydrogen-sulfide in the water column (Fig. 14b). This is
confirmed by a rise in FeT/Al and Co/Al ratios. An expansion of the OMZ,
possible due to intensified paleoproductivity and/or sea level rise, leads
to mobilization of Fe and Co from nearshore sediments. Thus,
enrichment in FeT and Co in the sediments is possible, when hydrogen
sulfide is present in the water column for sulfide precipitation.
Musavu-Moussavou and Danelian (2006) analyzed the radiolarian
abundances across OAE 2 at Site 1258 and Site 1261. The presence of
radiolarians at Site 1258 and to a lesser degree at the shallower Site
1261 below OAE 2 indicates, at least periodically, oxygenated surface
waters. During OAE 2, the absence of radiolarians at Site 1261 and only
rare occurrence at Site 1258 hint at the intensification of euxinic
conditions, while above OAE 2 radiolarians are present again, this time
with higher abundances at Site 1261 than at Site 1258. In marine
sediments Si derives either from the terrigenous detritus as alumino-
silicates, quartz or from a biogenous opal from siliceous plankton
(diatoms or radiolarians; Brumsack, 1989). Assuming an ‘average
Fig. 14. Simplified scheme of paleoenvironmental conditions as deduced from geochemical data before/after (a) and during (b) OAE 2.
323
shale’-like terrigenous background for C/T-black shales of Demerara
Rise the enrichment in Si indicates the presence of additional Si other
than present in the clay component. Owing to the absence of heavy
mineral related elements Hetzel et al. (2006) could exclude the
presence of excess quartz in Cretaceous black shales of Demerara Rise
and instead assumed a biogenous origin for the excess silica. We
suppose that the enrichment in Si shown in Fig. 13 represents Si
derived from radiolarian tests. The general pattern with slight
enrichment of Si below and above OAE 2 fits well with the findings
of Musavu-Moussavou and Danelian (2006).
Hardas and Mutterlose (2007) analyzed the calcareous nannofossil
assemblages of Site 1258 and 1260. They found highest absolute abun-
dances below OAE 2 at both sites. During OAE 2 the absolute abundance
decreases and also the species assemblages change. From the now
dominating species the authors conclude a higher bio-productivity.
Instead of cooler temperatures, as suggested by Forster et al. (2007) at
Site 1260 within OAE 2, Hardas and Mutterlose (2007) postulate a slight
increase in sea surface temperatures. They suggest a possible break-
down of water column stratification and thus a shallowing of the
324 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

nutricline. This fits into a picture of a euxinic water column and the overall sulfur cycle, similar to results observed previously in the Tarfaya
decline in total abundance of nannofossils. Basin.
Regarding the redox conditions at the sediment–water interface
According to the assumed high bioproductivity and the depletion in
Friedrich et al. (2006) suggest a strengthening of the OMZ during OAE
Mn, the C/T black shales of Demerara Rise are compatible with a
2, based on the benthic foraminifera assemblage at Sites 1258–1261.
situation encountered in modern coastal upwelling areas within an
Below OAE 2 the authors suggest anoxic to sometimes slightly
expanded OMZ. During OAE 2 a more euxinic situation was established
dysoxic bottom-water conditions at the shallower sites, whereas for the
with the presence of free hydrogen sulfide in the water column.
deepest Site 1258 more oxygenated but still dysoxic bottom waters were
proposed, possibly due its position below the OMZ. During OAE 2, the
Acknowledgements
total absence of benthic foraminifera hints to anoxic conditions, but
short-term re-populations may indicate bottom-water oxygenation. The We would like to thank the crew and scientific party of ODP Leg 207
authors find these events in the lower third of OAE 2 at all sites studied. for their kind support. This research used samples and/or data provided
Forster et al. (2007) correlate these occurrences with a cooling event at by the Ocean Drilling Program (ODP). ODP is sponsored by the U.S.
Site 1260. Benthic foraminiferal assemblages indicate continued oxygen- National Science Foundation (NSF) and participating countries under
deficient bottom-water conditions following OAE 2 with the exception of management of Joint Oceanographic Institutions (JOI), Inc. This contribu-
one short-term increase in oxygenation immediately above the OAE 2. tion has benefited from the thorough reviews by Tim Lyons and an
After ~0.5 Ma. more oxygenated bottom-water masses are postulated. anonymous reviewer. AH is grateful to Astrid Forster and Christian März
From geochemical data we suppose euxinic conditions during OAE 2. for valuable discussions, Knut Bernhardt for performing time series
The presence of benthic foraminifera indicates that the euxinic conditions analysis and Imke Notholt for EDX assistance. MEB wishes to thank Andrea
may not have been permanent. Evidence for the short-term complete re- Schipper for technical assistance and E. Clapton, N. Futado, C. Hynde, and
oxidation of the bottom water is not given by the geochemical data, J. Stone for acoustical inspiration during work on the manuscript. This
although peaks in Mn/Al several decimeters above the repopulation study was funded by Deutsche Forschungsgemeinschaft (IODP-SPP grants
events of benthic foraminifera at Site 1258 may indicate a shallowing of BR 775/16+17; BO 1584/2) and by Max Planck Society, Germany.
the OMZ thus introducing Mn to the sediment.
Addressing the same questions by different paleo-proxies may lead
to different results under certain circumstances. If sedimentation rates Appendix A
are low, and the amount of sample material required for certain analyses Quantification limit, precision and accuracy of analyzed elements
comprises a time-span in which several changes in depositional Element Method Quantification limit Precision SD (1σ) (rel%) Accuracy (rel%)
environment may have occurred, the chemical result would be an
ST IR-analyzer 0.56% 3.0 99.9
integrated signal due to homogenization of the sample. In contrast, TC IR-analyzer 1.22% 1.6 101.2
analyzing fossils might give only a snapshot of paleoconditions. TIC Coulometry 0.19% 2.3 99.8
Contrasting results for the same intervals may therefore hint to unstable Si XRF 1.94% 1.3 99.1–101.0
Ti XRF 0.03% 1.2 98.1–101.0
conditions. Forster et al. (2007) suggest such unstable conditions during
Al XRF 0.77% 1.6 98.7–100.6
OAE 2 at Site 1260. From our point of view a closer look is necessary, if FeT XRF 0.33% 1.2 98.7–100.6
and to what extent the presence of the “ash-like” layers, which were Mg XRF 0.26% 1.9 99.3–101.0
omitted here, may influence directly or by diagenetic effects results Ca XRF 0.80% 1.6 99.4–99.7
obtained in close vicinity to these layers. Na XRF 0.21% 5.7 90.1–100.6
K XRF 0.20% 2.6 95.5–100.4
P XRF 0.04% 6.5 98.6–108.8
5. Summary and conclusions As XRF 4 ppm 7.0 96.0–100.0
Ba XRF 77 ppm 2.5 98.8–102.6
From geochemical analysis the following conclusions regarding the Co XRF 9 ppm 8.1 93.7–95.4
Cr XRF 17 ppm 2.9 98.4–104.4
depositional environment of C/T black shales at Demerara Rise during
Cu XRF 21 ppm 6.6 94.0–102.2
OAE 2 can be drawn: Mn XRF 78 ppm 2.2 97.5–103.1
Mo XRF 14 ppm 6.0 94.1–104.3
• Elevated FeP/FeT, FeT/Al, and Co/Al values within the OAE 2 confirm Ni XRF 14 ppm 3.3 99.1–103.8
euxinic conditions but, at the same time, require a zone where Rb XRF 26 ppm 3.9 92.7–101.8
Sr XRF 120 ppm 9.7 101.0–102.2
reducing but non-sulfidic conditions enable Fe and Co mobilization
U XRF 5 ppm 10.9 109.0–110.2
in oxygen depleted nearshore sediments. V XRF 56 ppm 4.2 99.8–100.9
• The existence of an expanded oxygen-minimum-zone (OMZ) is Y XRF 8 ppm 5.4 98.5–109.5
demonstrated by extremely low Mn/Al ratios. Elevated Mn/Al ratios Zn XRF 33 ppm 3.9 95.1–102.4
are only seen in distinct horizons. Overgrowth of Mn-carbonates on Zr XRF 30 ppm 3.6 96.1–103.7

pre-existing carbonate tests seems to be possible under euxinic
conditions and elevated pore water alkalinities.
• Mo/Al, V/Al and Zn/Al ratios are generally high throughout the
investigated sequence, but a significant depletion is notable exactly
during OAE 2. The decrease in enrichment for these seawater derived
trace metals may reflect the global onset of black shale deposition
during OAE 2 and the rapid drawdown of the seawater TM reservoir
For stable isotope measurements, see section on Materials and methods.
Notes: Procedures and accuracy of all methods were checked with in-house reference
materials (IR-Analyzer: PS-S (n=286); coulometry: Loess (n=387); XRF: DR-BS (n=33), TW-
TUC (n=14) and PS-S, (n=11)). Quantification limit is defined as 6 times the maximum
standard deviation (1σ). Precision is defined as 100% times the best estimate standard
deviation (1σ) divided by the mean of the repeats. The maximum value is given. SD=standard
deviation. Accuracy is defined as 100% times the mean of the repeat analyses divided by the
expected value. For XRF the range of different reference material is given.

by the enlargement of euxinic depositional areas.

• The enrichment in phosphorus and barium points towards high bio-
productivity like in recent upwelling areas. Due to diagenesis driven by
the reducing conditions a quantitative interpretation is not possible.
• Besides fixation of sulfide as iron sulfide, organic matter acts as an
important sulfur trap during early diagenesis. During OAE 2 the amounts
of both, pyrite and organically bound sulfur increase. A negative shift in
the stable sulfur isotope curve during OAE 2 indicates changes in the
Appendix B. Identification of so-called “ash layers”
(see text for details)
(a) Profiles for Si/Al, Ti/Al and K/Al for Cenomanian/Turonian black
shales at Sites 1258 and 1260. Grey: OAE 2; dashed line: “ash layers”.
(b) Images of sediment intervals (available online from Erbacher et al.,
2004, doi:10.2973/odp.proc.ir.207.2004). Dashed line: “ash layers”.
A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328 325
326 A. Hetzel et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 302–328

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ST % 6.03 2.60 0.24
Bernstein, R.E., Byrne, R.H., 2004. Acantharians and marine barite. Marine Chemistry
SP % (n = 11) 1.67 0.79
86 (1–2), 45–50.
δ34SP ‰ (n = 4) −15.4 − 15.8
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TIC % 2.73 5.56 0.35 precipitation of marine barite. Journal of Marine Research 55 (3), 577–593.
TOC % 8.55 10.39 Bishop, J.K.B., 1988. The barite–opal–organic carbon association in oceanic particulate
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 329

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Abstract of “Climate-Ocean coupling off North-West Africa during the Lower Albian:
The Oceanic Anoxic Event 1b”☆
Peter Hofmann a,⁎, Isabel Stüsser a, Thomas Wagner b, Stefan Schouten c, Jaap S. Sinninghe Damsté c
a
Institute for Geology and Mineralogy, University of Cologne, Zülpicher Str. 49a, 50674 Köln, Germany
b
School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne, NE1 7RU, United Kingdom
c
Department of Marine Organic Biogeochemistry, NIOZ Royal Netherlands Institute for Sea Research, Post Office Box 59, 1790 Den Burg, The Netherlands

a r t i c l e i n f o a b s t r a c t

Keywords: High resolution records of organic and inorganic geochemical proxies document environmental changes
Oceanic Anoxic Event 1b during Oceanic Anoxic Event 1b for the Albian upwelling system at DSDP Site 545 Mazagan Plateau off NW
Black shale Africa. Sea surface temperature estimates based on TEX86 analyses show an abrupt rise by ~ 3 °C concurrent
Sea surface temperatures
with a more than 2-fold increase in accumulation rates for organic carbon and siliciclastic sediment
Upwelling system
components. Geochemical grain-size indicators (Si/Al and Zr/Al) indicate the influx of overall finer grained
sediment during the event. Our data suggest that the warming phase associated with OAE 1b resulted in an
attenuation of the NE trade wind system and a weakening of local upwelling conditions. Higher amounts of
precipitation over NW Africa and an associated higher continental run off may have supplied nutrients to the
eastern North Atlantic and fostered the production of organic matter and black shale deposition.
© 2008 Elsevier B.V. All rights reserved.

☆ The full version of this paper has been published in: Palaeogeography, Palaeoclimatology, Palaeoecology 262, 2008, 157–165.
DOI of original article: 10.1016/j.palaeo.2008.02.014.
⁎ Corresponding author. Fax: +49 221 4705149.
E-mail address: peter.hofmann@uni-koeln.de (P. Hofmann).

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.12.011
 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345

Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Temperature controlled deposition of early Cretaceous (Barremian–early Aptian)

black shales in an epicontinental sea
Jörg Mutterlose a,⁎, Sebastian Pauly a, Thomas Steuber b
a
Institut für Geologie, Mineralogie und Geophysik, Ruhr-Universität Bochum, Universitätsstr. 150, 44801 Bochum, Germany
b
The Petroleum Institute, PO Box 2533, Abu Dhabi, UAE

A R T I C L E I N F O A B S T R A C T

Article history: A continuous, 103m thick mudstone sequence of Barremian–early Aptian age, recently exposed in northern
Received 16 November 2007 Germany, has been logged and analyzed with respect to its macrofaunal content and its geochemistry (δ13C,
Received in revised form 6 April 2008 δ18O). Based on common belemnite and rarer ammonite findings a detailed biozonation has been established
Accepted 17 April 2008
covering the complete Barremian–early Aptian interval, including the mid early Aptian “Fischschiefer”, the
deposition of which occurred during Oceanic Anoxic Event 1a. Quite common throughout the sequence are
Keywords:
Laminated sediments
finely laminated black shales (Blätterton) with high TOC contents of up to 7%. These laminated black shales
Anoxic conditions with CaCO3 contents of up to 60% are interbedded with dark and carbonate-poor clays on the scale of
Barremian/Aptian decimeters to several meters. Oxygen depletion of bottom waters is indicated for the laminated intervals
Belemnites since these are barren of any benthic fossils.
Stable isotopes A salinity driven stratification of the water column during more humid periods was caused by a more intense
Cooling run-off from the nearby hinterland. This and increased surface water productivity are seen as a possible cause
for the lamination with observations being mainly based on micropalaeontological evidence (dinoflagellates,
calcispheres, calcareous nannofossils). Stable isotope studies (δ13C, δ18O) performed on belemnite guards
show δ13C values of 0‰ to 2‰ for the Barremian. A distinctive positive excursion of ~ 4‰ directly above the
early Aptian Fischschiefer correlates well with the global positive δ13C excursion of mid early Aptian age
following the Oceanic Anoxic Event 1a. This first record of the δ13C positive excursion from the Boreal Realm
therefore confirms the global nature of the signal. A shift in δ18O values of about 2‰ in the late Barremian–
early Aptian is interpreted as a temperature decrease by ~ 8°C. This cooling goes along with a shift from the
thick (up to 6.5m) early Barremian Hauptblätterton to thin (10cm to 20cm) laminites (Blätterton) in the late
Barremian. During the deposition of the Hauptblätterton very warm conditions caused a long lasting (N
500kyrs) stable water stratification. The cooler temperatures of the late Barremian reduced the stability of
the water stratification resulting in rather short termed alternations of thin laminites and dark clays. These
observations suggest a temperature controlled peak of anoxic conditions in the early Barremian
Hauptblätterton and subsequently short termed changes from anoxic to suboxic conditions in the late
Barremian and early Aptian.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Throughout the Barremian and early Aptian the region presently
occupied by the North Sea, the Netherlands, northern Germany, and
Poland formed the southern extension of a shallow marginal sea that
was connected to the Boreal–Arctic Sea in the north by an open sea
way (Fig. 1). This semi-restricted basin was characterized by the
deposition of more than 200m of clay- and mudstones with distinctive
laminated clay horizons (“Hauptblätterton”, “Blätterton”, “Fischschie-
fer”) occurring throughout the succession. These sediments rich in C-
org, reflect basin-wide anoxic to suboxic conditions, caused by a major
regression in latest Hauterivian to earliest Barremian times, which
⁎ Corresponding author.
E-mail address: joerg.mutterlose@rub.de (J. Mutterlose).
closed the former sea way to the south via Poland. The restricted
palaeogeographic setting throughout the Barremian and the earliest
Aptian resulted in the deposition of the finely laminated black shales.
Oxygen depletion of bottom waters is indicated for the laminated
intervals since these are barren of benthic fossils. They yield, however,
well preserved nektonic and planktonic organisms, as well as
terrestrial plant material (Mutterlose and Böckel, 1998; Mutterlose
and Bornemann, 2000).
The origin and genesis of these Barremian black shales have been
widely discussed in recent years (Mutterlose and Böckel, 1998). A
stratification of the water column due to periodically increased run-off
has been suggested as a possible cause with observations being mainly
based on micropalaeontological evidence (dinoflagellates, calci-
spheres, calcareous nannofossils). The most prominent of these
laminated horizons, the 5m to 6m thick Hauptblätterton of late

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.04.026
 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
Fig. 1. Paleogeographic map of the Barremian of NW Europe showing the sections and localities mentioned in the text. DB = Danish Basin, sNSB = southern North Sea Basin, cNB =
central Netherland Basin, LSB = Lower Saxony Basin, PB = Polish Basin. 1 = A39 section; 2 = cores Hoheneggelsen KB 40, KB 50; 3 = Gott and Moorberg sections.
early Barremian age, has recently been the subject of a detailed
geochemical study (δ13C, δ18O, TEX86, trace elements) interpreting this
marker horizon as a warm water event (Mutterlose, personal
communication). There are, however, no stable isotope data available
for the complete early Barremian–early Aptian interval, which might
shed light on the long-term climatic trend, which in turn may be used
to decipher the origin of the laminites.
A temporary road cutting in 2005 offered the opportunity to log
and sample a 103m thick fossiliferous succession covering the
complete lower Barremian–lower Aptian interval. Common belemnite
and rarer ammonite findings allowed for a detailed biozonation which
formed the base for further detailed isotope studies. The current paper
aims at reconstructing the palaeotemperature record for the Boreal
lower Barremian–lower Aptian by supplying stable isotope data (δ13C,
δ18O) from belemnite guards. Further on we want to use these findings
to better understand the genesis of the laminated clays and to describe
the environmental changes that occurred in the Barremian–early
Aptian seas.
2. Geological setting
2.1. Sediments
Marine sediments of early Barremian–early Aptian age have a
widespread distribution in northern Germany, the North Sea and to a
certain extent in northeast England, where they have been studied for
over a hundred years. During this period NW Europe was composed of
a number of basins (central Netherland Basin, Lower Saxony Basin,
Danish–Polish Basin, southern North Sea Basin), forming the southern
extension of the Boreal–Arctic Sea further to the north (Fig. 1).
Seaways towards the Tethys in the south did not exist during this
period. The Lower Saxony Basin formed the southernmost of these
basins, having a length of 280km and a width of 80km. In Barremian
and Aptian times the central parts of this basin were characterized by
331
continuous subsidence, and great thicknesses of shales and mud-
stones accumulated. Shallow water sediments, including sands and
iron-rich mudstones, were deposited along the margins of the basin in
the west, south and east. The evolution of the basin has been
described in detail (Schott et al., 1969; Michael, 1974, 1979; Kemper,
1979; Mutterlose, 1992; Mutterlose and Bornemann, 2000).
After a final transgressive peak in the latest Hauterivian [Simbirs-
kites (Craspedodiscus) discofalcatus ammonite Zone] significant
palaeogeographic and palaeoceanographic changes occurred at the
Hauterivian/Barremian boundary, and the overall character of the
Barremian succession in NW Europe is regressive (Rawson and Riley,
1982; Ruffell, 1991). A regression in the earliest Barremian led to
brackish–lacustrine conditions in central and southern Poland (Marek
and Racynska, 1979), isolating the North Sea and adjoining areas from
a marine sea way to the south.
A thick laminated marker horizon, the Hauptblätterton of late early
Barremian age, marks the establishment of anoxic conditions
throughout the Lower Saxony Basin, the remainder of the overlying
Barremian sequence consisting of only two main lithologies. Dark
clays and laminated marls form a clay–Blätterton alternation (Fig. 2).
The timing of the onset and the thickness variation of the Barremian
laminites allows for a differentiation of a basin centre and a basin
margin. In the basin centre earliest laminites occur already near the
Hauterivian–Barremian boundary interval, at the basin margin they
first appear in the late early Barremian (Hauptblätterton). While thin,
i.e. 10cm to 20cm thick laminites (Blättertone) are quite common
throughout the late Barremian of the basin centre, they are much rarer
at the basin margin. These patterns suggest that anoxic conditions
prevailed in the basin centre from latest Hauterivian time onward,
expanding onto the margins only in the late early Barremian (Fig. 3).
Detailed stratigraphical and geochemical data of the clay–
Blätterton alternation have been compiled by Benesch et al. (1998),
Bischoff and Mutterlose (1998), Hild and Brumsack (1998) and Littke
et al. (1998). The late Barremian dark clays contain an average of 2%
332 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
Fig. 2. Bio- and lithostratigraphy of the Barremian–Aptian in northern Germany.
Corg and they are poor in calcium carbonate which varies from 0% to
10% and decreases toward the top of the Barremian. The latest
Barremian depressa Clay (Fig. 2) has calcium carbonate values of 0% to
1%, being rich in pyrite and siderite. The laminites throughout the
Barremian are enriched in organic matter (2% to 7% TOC), their calcium
carbonate content ranges from 10% to 45%. The organic particles are
mainly composed of liptinites that formed from spores, pollen and
algae. The liptinites increase toward the top, with the Fischschiefer
being the most liptinite-enriched end member (90% to 95%) of the
anoxic sequence. Terrigenous organic matter (vitrinite and inertinite)
on the other hand is more common in the clay–Blätterton alternation.
The restricted palaeoceanographic conditions of the Barremian which
allowed the accumulation of these organic-rich sediments prevailed
into earliest Aptian time, as dark clays (Deshayesites bodei Clay) are
overlain by the Fischschiefer rich both in organic matter and calcium
carbonate (Fig. 2). Above the Fischschiefer, pale marls indicate a change
in the depositional environment to hemipelagic conditions. Named after
the common planktonic foraminifera Hedbergella, these Hedbergella
Marls correspond to the Gargasian Stage of the French subdivision.
Based on findings of different species of the belemnite Neohibolites, the
Hedbergella Marls can be subdivided into a lower (Neohibolites ewaldi
Marl), a middle (Neohibolites clava Marl) and an upper (Neohibolites
inflexus Marl) unit.
2.2. Palaeontology
While benthic organisms (foraminifera, macrofossils) are in
general rare throughout the Barremian–lower Aptian mudstone
sequence, phytoplankton (calcareous nannofossils, calcispheres, dino-
flagellates) and nektonic faunas (ammonites, belemnites, fish) are
quite common. The palaeogeographic and palaeoceanographic con-
figuration (Fig. 1) favoured the evolution of endemic species from
Tethyan ancestors. Among both nannofloras and faunas, endemic
species evolved simultaneously and became quite abundant. These are
associated with Boreal elements, whereas Tethyan forms are extre-
mely rare or absent.
Calcareous nannofossils are common in the lower Barremian, their
diversity and abundance decrease in the upper Barremian. The dark O.
depressa Clay of latest Barremian age is virtually barren, reflecting the
overall low CaCO3 content of these beds. Rich and diverse assemblages
 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
Fig. 3. Lithostratigraphic correlation of laminites of the basin margin and basin centre.
of calcareous nannofossils, consisting of up to 58 species, have been
listed from the Blätterton and the Fischschiefer (Mutterlose and
Harding, 1987; Habermann and Mutterlose, 1998). A distinctive
sequence of calcareous nannofossil species on the scale of 10μm,
described from the late early Barremian laminated Munk Marl Bed
(= Hauptblätterton) of the Danish Sector of the North Sea by Thomsen
(1989), implies that climatic/oceanographic changes in the Barremian
were effective enough to cause seasonal changes.
The non-laminated black clays and marls of the upper Barremian
and lower Aptian are poor in amorphous kerogen and relatively
impoverished in terrestrial palynomorphs (spores, pollen). On the
other hand dinoflagellates show both high diversity and high
abundance within these non-laminated sediments, reflecting a strong
marine signal. An average of 72 species of dinoflagellates has been
encountered (Below and Kirsch, 1997). The laminated sediments are
enriched in amorphous kerogen and in terrestrial palynomorphs. Both
Blätterton horizons and the Fischschiefer show strong influxes of
terrestrial matter in comparison to the black clays. The abundance and
diversity of dinoflagellates decrease in these sediments. Averages of
36 species were found in the Blätterton and 32 species in the
Fischschiefer. Within palynomorphs the Prasinophyta (Pterospermella,
Leiosphaera) show quite distinctive fluctuations. This group, which is
believed to indicate a reduced salinity of surface waters (Below and
Kirsch, 1997) is enriched in the laminites. Prasinophyta make up an
average of 24% of total organic matter in the Blätterton, whereas this
333
group is absent in most samples of the non-laminated facies. The data
gained from palynomorphs thus very clearly indicate a strong
terrigenous input, reduced salinity of surface waters, and a weaker
marine signal for the deposition of the laminites of the late Barremian.
In the marginal parts of the basin these phases of increased terrestrial
input are reflected by silt components. The non-laminated clays and
marls of the early Aptian in contrast record a stronger marine signal.
The calcispheres of the clay–Blätterton alternation are dominated
by obliquipithonelloid cysts, with coarse-crystalline forms being more
common than fine crystalline ones. These associations indicate cold
water conditions in a pelagic regime (Keupp and Mutterlose, 1994).
Barremian benthic foraminifera show a gradual decrease in
diversity and abundance over the succession, with agglutinated
foraminifera dominating in sediments of latest Barremian and early
Aptian age; tiny very thin-shelled calcareous foraminifera are rare. The
Hauptblätterton and Blätterton horizons yield extremely impover-
ished microfaunas; only a few species of ostracods and benthic
foraminifera are known from these beds (Michael, 1967). Rarely there
are more than 10 species in a sample.
The cephalopod faunas of the Barremian of NW Europe are
dominated by the belemnite family Oxyteuthididae (suborder
Belemnitina), a group which is restricted to the Boreal Realm. The
Oxyteuthididae are extremely common and the most useful index
fossils in the Barremian of NW Europe (Mutterlose, 1990). The species
succession of the Oxyteuthididae both in NW Germany and NE
334 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
England clearly shows an evolutionary lineage: Praeoxyteuthis
jasikofiana (Hauterivian–Barremian boundary interval)–Praeoxy-
teuthis pugio (earliest Barremian)–Aulacoteuthis spp. (late early
Barremian)–Oxyteuthis brunsvicensis (early late Barremian)–Oxy-
teuthis germanica (mid late Barremian)–Oxyteuthis depressa (latest
Barremian). O. depressa, the last species in the Barremian is the most
common macrofossil in the dark black clays of the basin facies (Fig. 4).
This Praeoxyteuthis–Aulacoteuthis–Oxyteuthis assemblage is endemic
to the southern North Sea (northeast England, northern Germany), it
differs from the assemblages of the Russian Platform and is unknown
from the Tethys.
A diverse and excellent preserved fish fauna has been described
from the Barremian laminites (Brahms, 1913) supporting the absence
of benthic organisms due to oxygen depletion of the bottom waters.
This diverse fish fauna is dominated by teleostei (13 species), ganoid
fishes are less common (6 species). The Fischschiefer owes its name to
the well preserved fossil fishes which have been described from
Helgoland (Taverne and Ross, 1973). Based on taphonomic observa-
tions these fishes were deposited in a lagoonal setting.
In conclusion the palaeontological data suggest anoxic (Blätter-
ton)–suboxic conditions (dark clay) of bottom waters in a semi-
restricted epicontinental sea, characterized by often endemic marine
floras and faunas. Variations of run-off caused changes of surface
water salinity with the laminites indicating a stronger input of
terrestrial matter. This implies that the anoxic conditions which
caused the deposition of the laminites went along with a periodically
stable halocline and increased surface water productivity of the
primary producers, which in turn resulted from seasonally increased
run-off from the nearby hinterland.
Fig. 4. Belemnite zonation of the Boreal Barremian.
3. Material
Material (bulk rock samples, belemnite guards) has been studied
from a road cutting of the motorway “A39” located three km east of
Braunschweig (northern Germany; coordinates: 52°14.819 N, 10°36.657
E to 52°14.845 N,10°36.322 E; Fig.1). Today, the road cutting is no longer
accessible, but when the samples were collected in 2005, a 103m thick
sequence of Barremian–early Aptian sediments was exposed. The age
assignment and biozonation of this succession employed here is based
on belemnites and ammonites (see Section 5.1).
The lower Barremian is characterized by 12.5m of mudstones,
which include 5.7m of finely laminated CaCO3 rich black shales at its
top. These finely laminated black shales yield a rich belemnite fauna
(Aulacoteuthis spp.), and are here assigned to the Hauptblätterton of
the Aulacoteuthis spp. belemnite zone (Fig. 5). The thickness of the
upper Barremian (Fig. 5) cannot be fixed exactly, due to a 5.5m thick
interval barren of index fossils near the Barremian/Aptian boundary. It
varies from 72.5m (last occurrence of the late Barremian belemnite
Oxyteuthis depressa in bed 165) to 78m (first occurrence of the early
Aptian ammonite Deshayesites deshayesi in bed 170). The upper
Barremian consists of dark clays and laminated mudstones containing
an abundant belemnite fauna assigned to the Oxyteuthis brunsvicensis,
Oxyteuthis germanica and O. depressa zones. The uppermost 12.5m of
the sequence which include dark clays, laminated mudstones, three
tuff horizons and pale marls is of early Aptian age, based on findings of
the belemnite Neohibolites ewaldi and the ammonite D. deshayesi.
A total of 119 bulk-rock samples, collected bed-by-bed, has been
studied from the 103m thick sequence for CaCO3, 83 samples for TOC
(Appendix A). A total of 89 belemnite guards has been collected bed-
 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
Fig. 5. Litho- and biostratigraphy of the A39 section showing the TOC- and CaCO3 values. P. p. = Praeoxyteuthis pugio, A. = Aulacoteuthis, O. b. = Oxyteuthis brunsvicensis, O. g. = Oxyteuthis germanica, O. d. = Oxyteuthis depressa, N. e. = Neohibolites ewaldi, D.
d. = Deshayesites deshayesi.

335
336 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345

Fig. 5 (continued ).
 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
Fig. 5 (continued ).
by-bed allowing for a detailed biostratigraphic zonation. Out of these,
68 guards have been analyzed for their trace elements and
subsequently for their stable isotope values (δ13C, δ18O).
4. Methods
4.1. Belemnite taxonomy
The taxonomic concept used for the belemnites is that of Mutterlose
(1983), and Mutterlose and Baraboshkin (2003). The species assignments
follow morphological aspects with individual species based on biometric
criteria. The various species of the Praeoxyteuthis–Aulacoteuthis–Oxy-
337
teuthis stock form an evolutionary lineage which passes from one another
with minor overlap of the individual species. The high abundance of these
taxa throughout the Boreal Barremian allows for a biometric–statistical
analysis of this group, resulting in more objective species criteria rather
than pure morphological descriptions. Praeoxyteuthis includes elongate
slender taxa without groove, Aulacoteuthis is defined by its slender form
and a ventral groove. Oxyteuthis includes rather stout ungrooved forms
with dorsoventral flattening of the guards increasing from O. brunsvicensis
via O. germanica to O. depressa (Fig. 4).
4.2. Bulk rock geochemistry
The CaCO3 content was measured by using the “Müller-Bombe”
(Müller and Gastner, 1971; accuracy ± 3wt.%). The bulk rock samples
(2.0g), which were dried and homogenized, were subsequently
dissolved with HCl (15%) in a glass bottle equipped with a manometer.
The CaCO3 content was calculated by the relative gas pressure increase
inside the glass bottle. TOC data were obtained by combustion of dried
bulk rock samples at ~ 1250°C. The evolving CO2, which corresponds
to the total carbon (TC) was measured coulometrically. The amount of
TOC was then calculated by using the CaCO3 and CO2 data by the
equation: TOC = (TC) − (CaCO3 ⁎ 0.12).
4.3. Belemnite geochemistry
A total of 68 belemnite guards was studied with respect to their trace
elements and stable isotope values (δ13C, δ18O). After boiling the guards
in water all specimens were split dorsoventrally along the “Klähnsche”
interface (see Ernst, 1964) by using a small chisel. Material (2mg) was
then removed from the split surfaces by using a microdrill (Proxxon
hand-held driller, 0.4mm tungsten drillbit). Since the δ13C and δ18O
values of Barremian belemnites do not show a significant ontogenetic
variation for oxyteuthid belemnites, one sample was taken from each
rostrum. The sampling took place halfway between the apical line and
the outer surface. Prior to stable isotope studies, each sample was
analyzed for trace element concentrations (Mg, Mn, Fe, Sr) using an ICP-
AES (SpectroCirosCCD). Owing to errors in weighing of samples, precision
of these results was ± 8% of the reported concentrations. Analytical
detection limits for Mn and Fe were 8ppm and 80ppm, respectively.
Stable isotope values (13C/12C, 18O/16O) were measured using a Finnigan
MAT 251 mass spectrometer combined with a Carbo Kiel device. All
reported δ-values refer to the PDB standard if no other standard is
indicated. Reproducibility of isotopic results (± 0.08‰ δ13C and ± 0.1‰
δ18O) was monitored by continuous analyses of standard materials.
Palaeotemperatures were calculated using the δ18O notation following
the equation of Epstein et al. (1953) andCraig and Gordon (1965), as
modified by Anderson and Arthur (1983):
T ½ C ¼ 16:0−4:14*ðδCaCO3 −δH 2 O½SMOW Þ
◯
þ 0:13*ðδCaCO3 −δH 2 O½SMOW Þ2 :
In this equation δH2O is the oxygen isotopic composition of
seawater from which the calcite was precipitated, referring to the
SMOW standard. Since the seawater δ18O value is related to ice
volumes and latitudinal gradients, different values have been used.
Today's world would ask for a δ18O value of 0‰ SMOW, an ice free
world which has been suggested for the Cretaceous requires a δ18O
value of − 1‰ SMOW (Shackleton and Kennett, 1975); both values
have been used in our palaeotemperature calculations (Appendix B).
Because of the difficulties in quantifying the impact of potential ice
volumes and latitudinally controlled evaporation in particular in
relative small marginal seas, more recent studies (e.g. McArthur et al.,
2007) only use δ18O data without referring to absolute temperatures.
We follow this approach, but list the calculated temperatures in
parenthesis for both seawater δ18O values (0‰; − 1‰).
338 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
5. Results
5.1. Palaeobiology and biostratigraphy
The most applicable biostratigraphic scheme of the Boreal
Barremian is based on belemnites, which are quite common and for
which a modern taxonomy exists. Out of the 89 guards collected from
the A39 section 80 specimens were assigned to the Praeoxyteuthis–
Aulacoteuthis–Oxyteuthis stock, four to Hibolithes minutus, endemic to
the Boreal Barremian. Five specimens were attributed to Neohibolites
ewaldi typical for the early Aptian. A detailed list of the species is given
in Appendix B. All zonal markers characteristic for the Barremian were
observed implying a complete, undisturbed sequence. Belemnite
guards were found both in the dark clays and in the laminites, species
of Aulacoteuthis occurring abundantly in the Hauptblätterton (Fig. 5,
Appendix B). These findings of belemnites in sediments of anoxic
origin, which are barren of any benthic organisms, exclude a
nektobenthic life style for Aulacoteuthis like that of recent Sepia. It
rather suggests a nektonic life like recent teuthids. This view is
supported by findings of arm hooks, which indicate a life as an active
predator, and TEX86 palaeothermometry data (Mutterlose, personal
communication). A constant offset of warmer TEX86 data and
relatively cooler δ18O belemnite signal by 4°C to 5°C during the
Hauptblätterton has been observed, which has been interpreted to
reflect temperature signals from two different depth habitats.
According to these interpretations Aulacoteuthis was a permanent
Fig. 6. Trace elements of belemnites from the A39 section.
swimmer living in subsurface waters of perhaps 50m to 150m (for
details see Mutterlose. personal communication).
Ammonites have been observed in the A39 section from bed 170
about 0.5m below the first Fischschiefer horizon. A total of 31
ammonites has been attributed to the genera Prodeshayesites, Deshaye-
sites, Aconeceras, Ancyloceras, Sanmartinoceras confirming an early
Aptian age. For a more detailed discussion of the early Aptian ammonite
faunas see Casey (1964), Kemper (1971, 1995) and Raisossadat (2004).
5.2. Bulk rock geochemistry
The CaCO3 values vary from 0% to 5% in the dark clays and from 8%
to 30% in the laminated black shales (Appendix A). These results are
consistent with previous data, which stated a maximum of 45% CaCO3
for the laminated sediments (Mutterlose and Böckel, 1998). Carbonate
is mainly contributed by calcareous nannofossils and calcispheres,
while both benthic and planktonic foraminifera are absent. The
benthic foraminifera are very rare or absent due to the anoxic bottom
water conditions (Michael, 1967), while planktonic foraminifera did
not yet occur in Barremian times in the Boreal Realm. The basal part of
the overlying Hedbergella Marl is marked by a remarkable change to
diverse and abundant assemblages of benthic and planktonic
foraminifera (Rückheim and Mutterlose, 2002).
The TOC values vary from 0.1% to 7%, lowest values were measured
in the tuff horizon 179. The TOC content of the Hauptblätterton ranges
from 0.6% to 4.3%, that of the Blättertone from 1.4% to 6.2%.
 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345 339

5.3. Trace elements of belemnites 5.4. Stable isotope data of belemnites

Concentrations of selected trace elements (Mg, Mn, Fe, Sr)
determined from the belemnites studied are shown in the cross-
plots of Fig. 6. Mg concentrations vary from 913ppm to 4898ppm
(Fig. 6, Appendix B), Mn concentrations from b 8ppm to 135ppm. Most
of the data points range from 1000ppm to 3000ppm for Mg (low-Mg-
calcite) and from 1ppm to 60ppm for Mn. For Mn, a threshold of
100ppm is considered to be critical for diagenesis (Steuber, 1999). Sr
concentrations vary from 1064ppm to 2238ppm, indicating a pristine
signal without diagenetic overprint. The critical threshold indicative
for the latter case is Sr concentrations below 1000ppm (Steuber,
2001). A trend of decreasing Sr concentrations and increasing Mn
concentrations would show a diagenetic alteration. Apart from four
belemnites (99/3, 109/2, 130/1, 140 base) all trace elements data
therefore indicate a pristine preservation of the belemnite skeletal
calcite and suggest that stable isotope values were not altered by a
significant diagenetic overprint.
Out of the 68 belemnites (Fig. 6, Appendix B) analyzed from the
early Barremian–early Aptian sequence, 64 specimens have been
considered for the following interpretation. The four specimens that
show high Mn and Fe concentrations (Fig. 6) are listed in Appendix B
(marked with an asterisk) but are not considered in Fig. 7.
The δ13C values of the belemnites delineate a threefold subdivision
of the section studied. In the lower 30m of the succession, rapid
changes from 0‰ to 2‰ are recorded within one horizon. Three
belemnite guards from a 10cm thick Blätterton horizon (bed 124) gave
a range from − 0.26‰ to + 1.62‰. Belemnites from laminites and clays
in most cases gave similar results. The middle part from 30m to ~ 80m
can be described as a plateau with most values ranging from + 1‰ to +
2‰. A significant increase to 4‰ above the early Aptian Fischschiefer
(~ 95m) marks the third interval.
The δ18O temperature estimates, assuming a seawater value of 0‰
SMOW (today) and − 1‰ SMOW (ice free Cretaceous), respectively

Fig. 7. δ13C and δ18O data from belemnites of the A39 section.
340 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
increase from sample 99/2 (17°C; 13°C) below the Hauptblätterton to
sample 100/4 (25°C; 20°C) in the basal part of the laminated black
shales with constant values around (25°C; 20°C) in the upper part of
the Hauptblätterton. The uppermost part of the Hauptblätterton has
recorded an increase of the δ18O values to − 1.8‰ (sample 100/14;
24°C; 19°C). It is in the directly overlying black clays that the δ18O
values show an increase to − 0.8‰ (sample 103/1; 20°C; 15°C). The
remainder of the O. brunsvicensis and O. germanica clay–Blätterton
alternation (12.5m to 30m above base) gave less negative δ18O values
of − 1.25‰ (115 mid; 21°C; 17°C) to 0‰ (112 base; 16°C; 12°C). These
show considerable fluctuations; within 20cm the δ18O values
decreases by nearly 0.8‰ from − 0.94‰ to − 0.17‰. The upper part
of the succession (30m to 103m above base), attributed to the upper
part of the O. germanica zone, the O. depressa zone and the N. ewaldi
zone, reveals a trend to values around ~ 0‰ (152/1; 16°C; 12°C). While
the δ18O values still vary from ~ 0‰ to − 1.3‰ (2m above 149; 21°C;
17°C) from 30m to 48m, the trend of the interval 48m to 103m is
rather stable with only minor variations.
Stable isotope patterns are often reflecting diagenetic alteration. In
our case the δ13C and δ18O values do not show parallel trends and are
not correlated statistically; these observations support the preserva-
tion of the original isotope values. The data clearly indicate relatively
warm conditions for the late early Barremian Hauptblätterton, a
gradual cooling throughout the early late Barremian and relative
stable cool conditions for the latest Barremian and early Aptian.
6. Discussion
6.1. Carbon isotope signature
The general trend of increasing δ13C values during the Barremian
corresponds to the pattern observed in bulk carbonate samples from
the Northern Tethys (Southern Alps; Weissert and Erba, 2004) and
apparently reflects changes in the global carbon cycle. The values for
the Barremian (0‰ to 2‰ δ13C) are consistent with data gained from
belemnites of Hauterivian age from Speeton, UK (Price et al., 2000;
McArthur et al., 2004), showing a similar range of 0‰ to 2‰ δ13C. They
fit well with two belemnite populations analyzed from the early late
Hauterivian and the mid Barremian of the Moorberg and Gott sections
about 40km further west (Fig. 1). A population of 121 specimens of the
Hauterivian Hibolithes jaculoides from a 20cm thick interval shows a
range from 0‰ to 2‰ with only one specimen obtaining a value of 3‰.
The mid Barremian Oxyteuthis population of 64 specimens, however,
has a much wider range from − 2‰ to 2.5‰. Our results agree with
published δ13C bulk rock data from hemipelagic sediments of the
Vocontian Basin, which range from 1‰ to 2‰ (Föllmi et al., 2006) and
also indicate a slight trend to higher values throughout the Barremian.
The δ13C data of the lower part of the A39 section (0m to 30m) show
considerable fluctuations of specimens found only 20cm apart by up
to 2‰ (Fig. 7; Appendix B). The relative negative values of the
belemnites from the Hauptblätterton and clay–Blätterton alternation
may reflect a regional signal of the semi-restricted Lower Saxony
Basin. The high amount of terrigenous organic matter of the laminites,
which is documented both by microapalaeontological evidence
(spores, pollen; see Section 2.2) and macrofloral findings, imply an
intensive freshwater input. Periodic changes in the freshwater input
may therefore explain the relative rapid shifts in the isotope signature
of the belemnites from − 0.26‰ to 1.6‰ within one 10cm thick
horizon. In analogy to their recent relatives, the Sepioidea and
Teuthoidea, which are the fastest growing marine invertebrates,
belemnites may be viewed as very fast growing with a life time of
1year to 4years (Mutterlose, personal communication). The rapid
ontogenetic growth of coleoids may thus explain the changes of the
δ13C values as a result of periodic changes of freshwater influx in a
semi-restricted system. More stable marine conditions prevailed in
the upper part of the Barremian (30m to 90m).
The positive δ13C excursion directly above the Fischschiefer (94.6m
to 96.9m) merits attention. Though the Fischschiefer clearly is a
regional phenomenon (Mutterlose and Böckel, 1998), it corresponds
stratigraphically to the Oceanic Anoxic Event 1a (= OAE 1a), which
correlates to the Italian “Selli” black shale event. The Selli level
observed in the Cismon section (Italy) and elsewhere is coeval with the
Fischschiefer, both successions showing a similar succession of
calcareous nannofossil events. In Italy, the Selli level is sandwiched
by the first occurrences (= FOs) of Chiastozygus litterarius/Rucinolithus
irregularis and the FOs of Rhagodiscus angustus/Eprolithus floralis (Erba,
1994). In northern Germany R. angustus has its FO within the
Fischschiefer while the FOs of E. apertior and E. floralis occur just
above this black shale (Bischoff and Mutterlose, 1998). The positive
δ13C excursion to 4‰ directly above the Fischschiefer which is based on
three belemnite guards corresponds to segment C6 and the lower part
of C7 (sensu Menegatti et al., 1998) observed in the Cismon section,
where the δ13Ccarb data (bulk rock) increase up to 4‰ in limestones
overlying the Selli level, below the FO of E. floralis (Weissert et al., 1998;
Hochuli et al., 1999). This event records a global perturbation of the
carbon cycle and has been observed from various sections in northern
Italy (Menegatti et al., 1998; Erba et al., 1999), Switzerland (Menegatti
et al., 1998; Wissler et al., 2003), France (Moullade et al., 1998;
Heimhofer et al., 2004), the Middle East (Vahrenkamp, 1996), the
central Atlantic (Herrle et al., 2004), the Pacific (Jenkyns, 1995) and
elsewhere. The positive δ13C excursion in the early Aptian of the A39
section is the first record of this event in northern Europe proving that
the carbon shift also affected the Boreal ocean. Of interest here is the
observation that while the belemnite δ13C isotopes signal a major
change in the carbon cycle associated with OAE 1a, the belemnite δ18O
signature does not show significant variations during this time
interval. This implies that that the δ13C-excursion is not related to a
significant temperature change but rather reflects an independent
global signal related to the carbon budget of the oceans.
6.2. Oxygen isotope values
From the early use of stable oxygen isotope signatures of
belemnites on it has have been discussed to which extent these
reflect the original temperature of the ocean water rather than a
diagenetic overprint. It is only in recent years that interest
concentrated on biological factors like varying depths habitat of
different genera/species, seasonal migration and ontogenetic varia-
tion of the life style which potentially influenced the δ18O signal.
The low trace element concentrations (Mg, Mn, Fe, Sr) of the
studied guards well below the critical threshold (see Section 5.3)
suggest a preservation of the original δ18O values, except for the four
specimens excluded in the discussion. The homogeneous, very fine
grained mudstone sequence impermeable for a significant pore water
flow does not support any diagenetic overprint by meteoric waters.
This is supported by the aragonitic preservation of the ammonite
shells. The belemnite guards do not show any signs of epi- or
endobenthic life indicating anoxic conditions of bottom waters and
the absence of early diagenetic overprint due to burrowing.
The belemnite species analyzed are, with the exception of four
specimens of H. minutus and five specimens of N. ewaldi, all included in
the Praeoxyteuthis–Aulacoteuthis–Oxyteuthis lineage. From this belem-
nite stock consecutive species evolved forming a phylogenetic lineage.
This evolutionary pattern may support the idea of a consistent life style
where the 11 individual species of this lineage occupied the same niche
over the ~ 6 my covering the Barremian. Since the δ18O values of the co-
occurring H. minutus correspond to those of the oxyteuthid lineage a
similar depth habitat may be derived for H. minutus from these data,
living in subsurface waters of perhaps 50m to 150m (see Section 5.1).
The oxyteuthid belemnites discussed here are restricted to the
Lower Saxony Basin and the adjoining North Sea; they are unknown
from the Tethys. The Barremian belemnite assemblages from other
 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345 341

Boreal areas (Greenland, Siberia), which are palaeobiogeographically belemnite faunas investigated because they are endemic to the
related to our study area, are different and only distinctly related. southern proto North Sea. Therefore we argue that the δ18O values
These biogeographic patterns exclude a major migration of the reflect the temperature conditions of a limited region. The isotope

Fig. 8. Model showing the depositional environment in the Barremian.

342 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345
patterns observed can therefore not be explained by major seasonal
changes or belemnite migration from one basin to another, but
seasonal migration within the proto North Sea seems possible.
In the A39 section the δ18O values increase from rather negative
(warm) values (~ − 2.0‰) in the late early Barremian (Hauptblätterton)
to relative positive (cool) data (~ 0‰) in the late Barremian and early
Aptian. Some of the data show quite a considerable variation of up to
~ 1.0‰ in belemnite guards collected close to one another. This
observation is supported by findings from a 56m thick mudstone
sequence of the Gott section 40km west of the A39 section (Fig. 1).
There the isotope data obtained from 22 specimens, collected from one
20cm thick horizon of the late early Barremian Hauptblätterton
(Mutterlose, personal communication), vary by 1.2‰ (= 4°C to 5°C)
from − 1.28‰ (21.5°C; 17.2°C) to − 2.42‰ (26.8°C; 21.5°C). This variation
may reflect short term climatic variations. These findings shed,
however, doubt on the usage of individual δ18O data for palaeotem-
perature interpretations; they rather suggest that general trends based
on more than two or three data points in a given bio-zone should be
used for palaeoclimatic interpretations. Despite these variations by
~ 1.0‰ (= 4°C) for different specimens of one species from one horizon
our data clearly indicate a cooling trend from a warm Hauptblätterton
period to a cool late Barremian–early Aptian. This is consistent with the
temperature trends derived from the isotopic composition of fish teeth
and rudist bivalves (Pucéat et al., 2003; Steuber et al., 2005) and
appears to reflect the global evolution of palaeoclimate.
Micropalaeontological observations of diversity patterns of calci-
spheres (Keupp and Mutterlose, 1994) from late Barremian–early Aptian
mudstones of two cores (Hoheneggelsen KB 40, KB 50; Fig. 1) approx.
25km west of the A39 section indicate cooler water conditions for the
clay–Blätterton alternation up to the base of the Fischschiefer. The
calcispheres are characterized by orthopithonelloids (25% to 60%) and
obliquipithonelloid (40% to 75%) cysts. The former is outer shelf dwellers
indicative for an open marine setting, the latter preferred neritic inner
shelf environments (Keupp, 1991). Within the obliquipithonelloids
changes of the abundance of coarsely and finely-crystalline morpho-
types reflect the availability of calcium carbonate. The clay–Blätterton
alternation with its general low carbonate content is clearly dominated
by coarsely-crystalline, single layered morphotypes. These coarse-
crystalline morphotypes make 80% to 90% of the late Barremian
obliquipithonelloid assemblages, with fine crystalline forms becoming
dominant in the Fischschiefer only (Keupp and Mutterlose, 1994). The
two different morphotypes (fine–coarse) are thought to be phenotypical
reactions depending on primary fluctuations of the carbonate content of
the ancient ocean water. Changes from fine–coarse and vice versa are
linked to changes of sea-surface temperatures, which in turn are
correlated with the solubility of CaCO3. The coarse-crystalline morpho-
types with their single walls indicate therefore cooler conditions, while a
dominance of finely-crystalline morphotypes with double layered walls
suggests a mineralization under warmer conditions. A trend towards
assemblages impoverished in calcareous phytoplankton is also reflected
by calcareous nannofossils. While the late early Barremian (Haupt-
blätterton) shows rich and diverse assemblages, diversity and abun-
dance decrease throughout the clay–Blätterton alternation only to attain
high values in the Fischschiefer again.
6.3. Palaeoceanographic implications
The palaeogeographic setting of the Lower Saxony Basin was quite
similar to that of the nowadays North Sea. Both reflect shallow
epicontinental seas with water depths probably not exceeding 200m,
being surrounded by landmasses considerably larger than these
marginal seas. The palynological observations of periodically reduced
surface water salinity go along with changes in the run-off from the vast
hinterland. During periods of increased run-off, as documented by high
Prasinophyta concentrations (Pterospermella, Leiosphaera) a stable
halocline with slightly reduced surface water salinities was established.
Simultaneously the primary productivity increased during these phases.
This in combination with generally warm conditions of 20°C to 25°C of
the lower water column according to the δ18O data (SMOW = 0) and 26°C
to 30°C following the TEX86 data (Mutterlose, personal communication)
caused a stable stratification preventing any oxygenation of the bottom
waters in this quasi lagoonal system. The δ13C values vary considerably
from 0‰ to 2‰ in the lower and mid Barremian, less so in the upper
Barremian, where they range from 1‰ to 2‰. In general the Barremian
δ13C values are significantly lower than those of the early Aptian
excursion, the latter reflecting the accelerated transfer of light 12C from
the oceans to the sedimentary carbon reservoir.
The discussed Barremian cooling trend may help in explaining the
thickness variation, as well as the stratigraphic and spatial patterns of
the laminites. The 5m to 6m thick Hauptblätterton of the early
Barremian, which is present throughout the Lower Saxony Basin, goes
along with a warm and stable period, allowing for a stratification of the
water column over a relative long time period. This warmest phase of the
Barremian marks the peak of laminite sedimentation, which occurred
both at the basin margin and in the basin centre (Fig. 8). The subsequent
cooling trend throughout the late Barremian–early Aptian caused a
change towards a more instable stratification of the water column. This
in turn caused a more regular break down of the stratification resulting
in much thinner laminates interbedded with dark clays. The lithological
changes from laminite to clay mirror slight variations in the oxygenation
of the bottom waters from anoxic to suboxic, reflecting shifts from
warm-humid (increased run-off, reduced surface water salinity,
increased productivity) to more cool-arid conditions (reduced run-off,
instable water stratification, normal productivity). The overall restricted
conditions in this marginal basin, however, did not allow a major
exchange of water masses through Barremian–early Aptian times.
7. Conclusions
A continuous, 103m thick mudstone sequence of Barremian–early
Aptian age, recently exposed in northern Germany, has been logged and
analyzed with respect to its macrofaunal content and its geochemistry
(δ13C, δ18O). The palaeontological data suggest anoxic (Blätterton)–
suboxic conditions (dark clays) of bottom waters in a semi-restricted
epicontinental sea, characterized by often endemic marine floras and
faunas. Short termed variations of run-off caused changes of surface
water salinity and primary productivity with the laminites indicating a
stronger input of terrestrial organic matter. This implies that the anoxic
conditions which caused the deposition of the laminites went along
with a periodically stable halocline which in turn resulted from
seasonally increased run-off from the nearby hinterland.
Short termed variations of the δ13C signal from belemnites of up to
2‰ are explained by periodical variations of the influx of dissolved
inorganic carbon with low δ13C values from the nearby hinterland.
The distinctive positive excursion of ~ 4‰ directly above the early
Aptian Fischschiefer correlates well with the Tethyan positive δ13C
excursion of late early Aptian age above the Oceanic Event 1a. Also, the
general trend of increasing δ13C values during the Barremian corre-
sponds to data from Tethyan deposits so that the data from the Boreal
Realm — despite its restricted palaeoceanographic conditions — largely
reflect global perturbations in the carbon cycle.
The high resolution δ18O record gained from belemnite guards of the
genera Praeoxyteuthis, Aulacoteuthis and Oxyteuthis throughout a
complete sequence of Barremian–early Aptian mudstones clearly
reflects negative (= warm) values (~ − 2‰) for the early Barremian.
The values increase by approximately 2‰ to values around 0‰
indicating a temperature decrease by ~ 8°C. This late Barremian–early
Aptian cooling has been observed in Tethyan sections as well, and is
consequently considered to reflect a global trend.
The late Barremian–early Aptian cooling goes along with a shift
from thick, up to 6.5m thick laminites (Hauptblätterton) in the early
Barremian to thin 10cm to 20cm thick laminites (Blätterton) in the late
 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345 343

Barremian. During the early Barremian Hauptblätterton very warm (continued)A (continued)
Appendix
conditions caused a long lasting (N 500kyrs) stable water stratification, Sample no Lithology CaCO3 [%] TOC [%]
while the cooler temperatures of the late Barremian reduced the 146/2 Clay 1.89
stability of the halocline resulting in rather short termed changes of 146/3 Clay 0.00 2.14
thin laminites and dark clays. These observations suggest a tempera- 146/4 Clay 5.66
146/5 Clay 5.66 2.80
ture controlled peak of anoxic conditions in the early Barremian 148/1 Clay 8.30 1.31
(Hauptblätterton) and subsequently short termed changes from 148/2 Clay 3.77
anoxic to suboxic conditions in the late Barremian and early Aptian. 148/3 Clay 15.09
Our findings also suggest that individual belemnite δ18O data 148/4 Clay 7.92 1.13
150/1 Clay 9.43 1.03
should not be used for palaeotemperature interpretations, since
150/2 Clay 1.89 1.09
different specimens from a single layer show a δ18O variation of up to 152/1 Clay 3.77 2.01
~ 1.0‰ (~ 4°C). For interpretations of general palaeoclimatic trends 155/1 Clay 1.89 1.98
more than two or three data points in a given bio-zone should be 155/2 Clay 4.15 1.79
therefore used in future studies. Secondly, palaeobiological (way of 157/1 Clay 1.89 2.62
157/2 Clay 2.26
life) and taxonomical aspects need to be accounted for. We supply 157/3 Clay 0.94 1.25
evidence that the oxyteuthid belemnites were nektonic, active 158/1 Concretion 6.42 6.68
swimmers living in water depths of 50m to 150m. 159/1 Clay 1.89 2.05
159/2 Clay 0.00
159/3 Clay 0.00 3.77
Acknowledgments
159/4 Clay 0.00
159/5 Clay 0.00 3.64
We are grateful to K. Wiedenroth for his support during fieldwork. 161/1 Clay 0.00 2.00
U. Heimhofer stimulated our discussions with valuable comments. 161/2 Clay 0.00
Constructive reviews by K. Föllmi and an anonymous reviewer 161/3 Clay 0.00 1.95
161/4 Clay 0.00
improved the manuscript substantially. Financial support by DFG 161/5 Clay 0.00 3.01
(MU 667/28-1) is acknowledged. 161/6 Clay 0.00
161/7 Clay 11.32
Appendix A 161/8 Clay 7.17
161/9 Clay 7.17
161/10 Clay 11.70 6.19
List of bulk rock samples, TOC- and CaCO3 data from the A39 section 162/1 Concretion 35.85 7.00
Sample no Lithology CaCO3 [%] TOC [%] 163/1 Clay 0.00 4.00
163/2 Clay 4.53
99/7 Clay 18.87 0.84
163/3 Clay 0.00 3.15
99/6 Clay 26.42
163/4 Clay 0.00
99/5 Clay 14.91 2.47
163/5 Clay 0.00 2.52
99/4 Clay 14.15
165/1 Clay 12.08 6.88
99/3 Clay 11.32 0.07
165/2 Clay 0.00
99/2 Clay 6.60 1.29
165/3 Clay 7.92
99/1 Clay 42.08 4.89
165/4 Clay 26.42
100/1 Laminite; HBt. 7.17
165/5 Clay 0.00 0.41
100/2 Laminite; HBt. 18.87 4.29
165/6 Clay 0.00
100/3 Laminite; HBt. 26.04
165/7 Clay 0.00
100/3b Laminite; HBt. 10.57
165/8 Clay 15.47
100/4 Laminite; HBt. 12.08 1.54
165/9 Clay 0.00 1.46
100/5 Laminite; HBt. 28.30
167/1 Clay 3.77 1.29
100/6 Laminite; HBt. 26.42 3.87
169/1 Clay 2.83 0.84
100/7 Laminite; HBt. 24.60
169/2 Clay 1.89
100/8 Laminite; HBt. 24.53
169/3 Clay 7.55 0.81
100/9 Laminite; HBt. 17.92 3.23
171/1 Clay 8.30 2.02
100/10 Laminite; HBt. 15.47
172/1 Fischschiefer I 25.66 6.12
100/11 Laminite; HBt. 13.21
173/1 Clay 5.28 0.49
100/12 Laminite; HBt. 23.58 3.78
173/2 Clay 4.91 0.63
100/13 Laminite; HBt. 9.43 0.59
174/1 Fischschiefer II 30.94 6.03
101/1 Clay 9.43 4.41
174/2 Fischschiefer II 54.72 4.60
102/1 Laminite; Blätterton 10.38 1.78
174/3 Fischschiefer II 56.60 3.38
103/1 Clay 15.09
174/4 Fischschiefer II 58.49 2.63
105/1 Clay 9.43 0.70
175/1 Concretions 75.47 0.27
106/1 Clay 25.00
176/1 Marl 62.26 0.59
107/1 Laminite; Blätterton 15.09 5.51
176/2 Marl 11.70
108/1 Clay 15.09 1.81
176/3 Marl 42.83 0.80
109/1 Laminite; Blätterton 15.09 2.75
176/4 Clay 10.57
109/2 Laminite; Blätterton 12.64 1.42
176/5 Clay 9.06 0.16
112/1 Clay 15.09 2.31
176/6 Clay 7.17
117/1 Laminite; Blätterton 15.09 4.94
176/7 Clay 7.55 0.46
124/1 Laminite; Blätterton 7.55 3.61
177/1 Tuff 5.28 0.34
125/1 Clay 4.91 2.44
178/1 Clay 5.66 0.22
127/1 Clay 4.15 2.28
179/1 Tuff 0.00 0.03
132/1 Laminite; Blätterton 0.00 5.01
180/1 Clay 6.98 0.99
134/1 Laminite; Blätterton 0.00 6.06
181/1 Tuff 0.38 0.28
138/1 Laminite; Blätterton 0.00 6.23
182/1 Clay 4.15 0.28
141/1 Clay 0.00 5.20
183/1 Tuff 3.77 0.28
145/1 Clay 3.77 1.77
184/1 Clay 4.15 0.36
145/2 Clay 4.34 1.68
184/2 Clay 6.23 0.35
146/1 Clay 19.06 4.23
185/1 Marl 3.77 0.12
344 J. Mutterlose et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 330–345

Appendix B (continued)B (continued)

Appendix
T [°C]
Geochemical data from Barremian belemnites, investigated for m Sample belemnite Fe Mg Mn Sr δ13C δ180 δw = δw = δw =
stable carbon, oxygen isotopes (δ13C, δ18O) and trace elements. above no. species [ppm] [ppm] [ppm] [ppm] 0 −0.5 −1
Palaeotemperatures reconstructed from δ18O (T°C). The samples base
marked with an asterisk show high trace element concentrations 22.4 ⁎130 O. germanica 182 1436 107 1647 1.25 −0.38 18 16 13
and have not been considered in Fig. 7. [1]
26.1 138/1 O. germanica 105 1389 34 1486 1.98 −0.39 18 16 14
26.2 ⁎140 O. germanica 237 2821 105 1803 1.81 −0.1 16 14 12
T [°C] base
31 145/1 O. 9 1449 2 1725 1.14 −0.29 17 15 13
m Sample belemnite Fe Mg Mn Sr δ13C δ180 δw = δw = δw =
−0.5 −1 brunsvicensis
above no. species [ppm] [ppm] [ppm] [ppm] 0
31.3 145/2 O. 227 2109 33 1788 1.09 −0.81 19 17 15
base
brunsvicensis
3.8 ⁎99/3 P. pugio 380 4898 49 2074 1.19 0.05 16 14 12 33.5 3.5m O. 76 1478 12 1675 1.89 −0.04 16 14 12
4.7 1.3m Hibolites? 48 1240 4 1568 1.36 −0.15 17 15 13 above brunsvicensis
below top
top 99 144
5.2 99/2 P. pugio 7 2479 10 2238 −0.04 −0.2 17 15 13 34.1 146/1 Oxyteuthis 119 1673 47 1573 1.95 −0.08 16 14 12
5.2 0.8m P. pugio 105 1487 8 1630 1.8 0.42 14 12 10 sp.
below 36.8 146/2 O. germanica 105 1658 34 1547 2.65 − 0.5 18 16 14
base 37 146/3 O. germanica 291 1104 48 1457 3.43 −0.57 18 16 14
100 37.7 146/4 O. germanica 131 1490 17 1777 1.5 −0.78 19 17 15
5.8 0.2m A. 138 1392 4 1752 1.1 −0.2 17 15 13 38.2 146/5 O. depressa 83 2488 3 1734 1.19 −0.09 16 14 12
below speetonensis 41 148/1 O. depressa 198 1318 34 1466 1.87 −0.08 16 14 12
base 42.3 148/2 O. germanica 99 2271 1 1491 0.52 −0.96 20 18 16
100 42.6 148/3 O. germanica 197 2712 16 1839 0.54 −0.44 18 16 14
5.9 99/1 P. pugio 17 1383 3 1874 0.36 −0.41 18 16 14 43.7 148/4 O. germanica 108 2156 3 1450 1.13 −1.1 21 19 16
7.5 100/3b A. ernsti 195 1395 19 1740 1.57 −1.16 21 19 17 46 150/1 O. depressa 186 2365 19 1824 1.66 −1.09 21 18 16
7.7 100/4 A. compressa 21 2845 2 2036 0.84 −2.03 25 23 20 47.8 2.0m O. depressa 99 1269 1 1446 1.93 −1.28 21 19 17
11.2 100/12 A. descendens 33 2057 1 1877 0.69 −2.01 25 23 20 above
12.2 100/14 A. compressa 92 1494 4 1904 1.51 −1.79 24 22 19 top
13.7 1.2m Aulacoteuthis 24 1521 4 1626 1.6 −0.77 19 17 15 149
above sp. 48.7 150/2 O. germanica 81 1807 1 1465 2.2 −0.31 17 15 13
top 50.2 152/1 O. depressa 149 1632 3 1595 1.6 −0.07 16 14 12
100 55.9 155/2 O. depressa 198 1856 3 1404 1.56 −0.18 17 15 13
14.3 103/1 O. 171 885 1 1064 1.39 −0.83 20 17 15 59.8 157/1 H. minutus 215 1652 3 1411 1.37 0.22 15 13 11
brunsvicensis 60.6 157/2 H. minutus 254 1899 2 1358 2.12 0.05 16 14 12
16.5 108/1 O. 152 1684 4 1554 1.07 −0.84 20 17 15 61.5 157/3 O. depressa 92 1469 1 1546 1.73 −0.15 17 15 13
brunsvicensis 61.8 158/1 H. minutus 99 1274 3 1276 1.62 0.22 15 13 11
17.4 0.1m O. 188 1623 21 1635 0.14 −1.07 21 18 16 74.8 0.1m O. depressa 95 913 33 1336 2.03 −0.39 18 16 14
below brunsvicensis below
top 110 base
17.5 ⁎109/2 Oxyteuthis sp. 3343 3331 135 1297 −2.53 −3.17 30 28 26 162
18.3 112 O. 232 2189 56 1566 0.53 −0.07 16 14 12 75.9 163 O. depressa 149 1652 5 1436 1.12 −0.55 18 16 14
base brunsvicensis mid
18.4 112/1 O. 328 2441 12 1592 0.35 −0.63 19 17 14 76.8 163/2 O. depressa 119 1024 2 1366 0.91 −0.11 16 14 12
brunsvicensis 77.6 163/3 O. depressa 382 1344 31 1158 1.53 0.21 15 13 11
19.4 115 O. 173 1671 27 1878 1.46 −0.94 20 18 16 83.9 165/6 O. depressa 120 1545 6 1224 2.16 0.19 15 13 11
mid brunsvicensis 84.6 2.3m O. depressa 107 968 6 1225 2.2 0.21 15 13 11
20.1 118 O. 97 1826 16 2109 0.29 −1.25 21 19 17 below
mid brunsvicensis base
20.2 120 O. 79 1368 10 1764 0.43 −0.94 20 18 16 166
base brunsvicensis 94.6 0.1m N. ewaldi 179 1832 23 1284 3.61 −0.01 16 14 12
20.3 121 O. 318 1601 26 1653 1.53 −0.17 17 15 13 above
mid brunsvicensis top 175
21.2 124 O. 31 1536 4 1627 1.62 −0.4 18 16 14 95.3 176/3 N. ewaldi 180 1809 28 1404 4.02 0.31 15 13 11
mid brunsvicensis 96.9 176/6 N. ewaldi 74 1461 8 1366 4.12 −0.35 17 15 13
21.2 124 O. 38 1598 9 1723 1.59 −0.39 18 16 14 97.7 176/7 N. ewaldi 134 2841 6 1329 1.75 0.15 15 13 11
brunsvicensis
21.2 124/1 O. 172 2094 59 2088 −0.26 −0.79 19 17 15
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Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / p a l a e o

Late Pliensbachian–Early Toarcian (Early Jurassic) environmental changes in an

epicontinental basin of NW Europe (Causses area, central France): A
micropaleontological and geochemical approach
Samuel Mailliot a, Emanuela Mattioli a,⁎, Annachiara Bartolini b, François Baudin c,
Bernard Pittet a, Jean Guex d
a
UMR 5125 PEPS, CNRS, France; Université Lyon 1, Campus de la DOUA, Bâtiment Géode, 69622 Villeurbanne Cedex, France
b
UMR 5143, CNRS, France; Muséum National d'Histoire Naturelle, USM 203, 8 rue Buffon CP 38 75231 Paris cedex 05, France
c
Université Pierre et Marie Curie-Paris6 and UMR 7072 Tectonique, CNRS, CP 117, 4 place Jussieu 75252 Paris Cedex 05, France
d
Institut de Géologie et Paléontologie, Université de Lausanne, Anthropole, CH 1015 Lausanne, Switzerland

A R T I C L E I N F O A B S T R A C T

Article history: We present an integrated work based on calcareous nannofossil and benthic foraminiferal assemblages, and
Received 30 November 2007 geochemical analyses of two Upper Pliensbachian–Lower Toarcian sections located in the central-South
Received in revised form 28 May 2008 France. The studied sections, Tournadous and Saint-Paul-des-Fonts, represent the proximal and the distal
Accepted 28 May 2008
part, respectively, of the Jurassic Causses Basin, one of the small, partly enclosed basins belonging to the
epicontinental shelf of the NW Tethys. At the transition from Late Pliensbachian to Early Toarcian, the
Keywords:
Causses Basin recorded an emersion in response to the global sea-level fall. Our data indicate severe
Calcareous nannofossils
Benthic foraminifers
environmental conditions of marine waters, including salinity decrease and anoxia development, occurring
Organic matter in the Early Toarcian. The acme of this deterioration coincides with the Early Toarcian Anoxic Event (T-OAE)
Carbon and oxygen stable isotopes but, due to the restricted nature of the basin, anoxia persisted until the end of the Early Toarcian, mainly in
Pliensbachian/Toarcian the deeper parts of the basin. The micronutrients and organic organic-matter fluxes were probably high
Toarcian Anoxic Event (T-OAE) during the entire studied time interval, as shown by nannofossil and foraminiferal assemblages. However,
nannoplankton production drastically decreased during the T-OAE, as demonstrated by very low nannofossil
fluxes, and only taxa tolerant to low-saline surface waters could thrive. At the same time, benthic
foraminifers temporarily disappeared in response to sea-bottom anoxia. Our study demonstrates that
environmental changes related to the T-OAE are well-recorded even in small, partly enclosed basins of NW
Europe, like the Causses Basin. Within this area, the effects of global changes, like sea sea-level and
temperature fluctuations, are modulated by local conditions mainly controlled by the morphology of the
basin.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
The Early Toarcian is marked by major environmental perturba-
tions. In many epicontinental basins, organic-rich sediments are
recorded that are interpreted as deposited under anoxic conditions.
The widespread record of such deposits led Jenkyns (1988) to
interpret the Early Toarcian anoxia as a global event (T-OAE). Anoxia
was temporarily spreading into the photic zone, as indicated by the
presence of biomarkers of green sulphur bacteria in some black shales
(Schouten et al., 2000; Schwark and Frimmel, 2004; Pancost et al.,
2004; van Breugel et al., 2006). The organic-rich sediments are
associated to a pronounced negative excursion in δ13C of both marine
(bulk carbonate, brachiopod calcite, organic matter, and specific
organic compounds; Jenkyns and Clayton, 1986; Schouten et al., 2000;
⁎ Corresponding author.
E-mail address: emanuela.mattioli@univ-lyon1.fr (E. Mattioli).
Jenkyns et al., 2001; Röhl et al., 2001; Jenkyns et al., 2002; van Breugel
et al., 2006; Emmanuel et al., 2006; Suan et al., 2008a), and
continental material (fossil wood, Hesselbo et al., 2000, 2007)
recorded in the Exaratum Ammonite Subzone that reflects major
perturbations in the global carbon cycle. In the rest of this account, we
refer to as T-OAE the stratigraphic interval corresponding to enrich-
ment in organic matter of the sediments and to the carbon isotope
negative excursion. This interval, according to various authors,
corresponds to the Exaratum Ammonite Subzone (Jenkyns and
Clayton, 1997; Hesselbo et al., 2000; Bailey et al., 2003) and to the
C. superbus nannofossil zone (Mattioli et al., 2004; Mailliot et al.,
2006).
Faunal extinctions in the marine realm occurred concomitant with
the T-OAE, but also at the Pliensbachian/Toarcian boundary (Little and
Benton, 1995; Harries and Little, 1999; Pálfy and Smith, 2000; Wignall,
2001; Cecca and Macchioni, 2004; Wignall et al., 2005). The T-OAE
may represent the acme of a longer-term environmental crisis

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.05.014
 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364 347

(Wignall et al., 2006). An important cooling of seawaters occurred in
the Late Pliensbachian, as inferred by oxygen isotope ratio and Mg/Ca
measured on belemnite rostra (McArthur et al., 2000; Bailey et al.,
2003; Rosales et al., 2004; van de Schootbrugge et al., 2005a,b), and
δ18O of brachiopod shells (Suan et al., 2008a). A significant marine
regression and emersions are recorded between the end of the
Pliensbachian and the base of the Toarcian in various western Tethyan
settings. This record has been interpreted as evidence for glacio-
eustatism (Guex et al., 2001; Morard et al., 2003).
This study aims to reconstruct the environmental changes
occurred in a time interval spanning the Late Pliensbachian and the
Early Toarcian. We present here an integrated study on planktonic
micro-organisms (calcareous nannofossils), benthic fauna (foramini-
fers), organic matter and stable isotopes from two sections, Tourna-
dous and Saint-Paul-des-Fonts, located in the Causses Basin (central-
South France). This basin, that was part of the NW Europe epi-
continental shelf of the western Tethys, recorded the sea-level
changes occurring in the studied interval (Trümpy, 1983). Sea-level
variations were evaluated on the basis of the analysis of sedimentary
structures observed in the two studied sections. This integrated
approach enabled us to reconstruct the evolution of the entire water
column conditions in terms of productivity and oxygenation across
the T-OAE.
2. Geological overview
The study area is located in the central-South France (Fig. 1). The
Causses Basin was a small, partly enclosed, intracratonic basin that
was part of the epicontinental seas at the West of the Tethys Ocean, at
a palaeolatitude comprised between 25 and 30° N (Fig. 1a). It was

Fig. 1. (a) Palaeogeographic map of the western Tethys (European realm) re-drawn after Bassoulet et al. (1993). The study area (central-South France) was located in the wide
epicontinental shelf of the NW Tethyan margin. (b) Simplified geologic map of the Causses Basin (after Trümpy, 1983) showing the location of the two studied sections: Tournadous
(TND) and Saint-Paul-des-Fonts (SPF).
348 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
located between the southern part of the French Massif Central and
the northern part of the Montagne Noire (Fig. 1b). The basin was
bounded by Hercynian crystalline rocks, belonging to different units of
the Massif Central, namely the Rouergue to the West, the Cevennes to
the East and Aubrac to the North (Trümpy, 1983). The morphology of
the basin was largely controlled by the late Hercynian structural
evolution. In the Early Jurassic, an extensional tectonic phase
reactivated some NNE–SSW normal faults (Arthaud and Matte,
1975). Subsidence was more pronounced in the central part of the
basin. The thickness of the Lower Jurassic succession strongly varies
from the basin margins to the depocenter, for instance the Toarcian
deposits vary from 15 cm to 15 m in the different localities (Morard,
2004). The sediments deposited on the margins of the basin are also
characterized by the presence of repeated hiatuses (Trümpy, 1983).
Two sections have been analysed in this study (Fig. 1b), namely
Tournadous (TND, very proximal) and Saint-Paul-des-Fonts (SPF,
more distal). The study interval corresponds to the Lower Pliensba-
chian Marnes de Villeneuve Fm. (Trümpy, 1983) and the Lower
Toarcian Schistes carton Fm. (Fig. 2). The Marnes de Villeneuve Fm. is
represented by dark marls with rare, interbedded limestone beds
often bioturbated and laterally discontinuous (Trümpy, 1983), inter-
preted as diagenetic in origin (Morard, 2004). A hard-ground enriched
in oxidized oxidised and phosphatized material, corroded belemnite
rostra, and fossil wood marks the Pliensbachian/Toarcian boundary.
This level corresponds to a hiatus (Trümpy, 1983) and is interpreted
here as an emersion surface. The Lower Toarcian Schistes carton show
finely laminated shales at the base (Schistes Papyracés according to
Monestier, 1921), and contain some detritic beds, enriched in silty
material, showing Hummocky Cross Stratification (HCS). One of these
beds is rich in fish remains (Leptolepis bed, Trümpy, 1983; Fig. 2) and is
present across the whole basin. Ammonites, belemnites, small
bivalves, and fish remains are frequent in the Schistes carton (Trümpy,
1983). The two sections are precisely correlated by means of
ammonite and calcareous nannofossil biostratigraphy, and lithostrati-
graphy (Fig. 2).
3. Materials and methods
3.1. Geochemistry
3.1.1. Carbonate and organic-matter content
The samples (51 for TND and 70 for SPF; Figs. 3 and 4) were cleaned
and dried in an oven at 90 °C for 24 h, before they were powdered in a
rotating disc mill. Total carbon (TC, wt.%) was determined using a LECO
IR 212 analyser by combustion of 100 mg of sample up to 1050 °C,
without previous decarbonatation; the resulting CO2 was quantified by
infrared detector. Calcium carbonate content (CaCO3, wt.%) was
determined using a calcimetric bomb by HCl digestion of 100 mg of
sample; the resulting CO2 was determined by pressure measurement.
Total organic carbon content (TOC, wt.%) was calculated by determin-
ing the difference between total carbon and carbonate carbon,
assuming that all carbonate is pure calcite and represents the unique
source of inorganic carbon. The precision for these analyses is ±0.5%
for calcium carbonate and ±0.1% for total and organic carbon.
Information on the type and thermal maturity of the organic
matter was obtained using Rock-Eval ® pyrolysis with an Oil Show
Analyser device (Vinci Technologies) under standard conditions (see
all details about Rock-Eval pyrolysis and parameters in Espitalié, 1993).
The parameter S2 is the amount of hydrocarbon released during step-
Fig. 2. Litho- and biostratigraphy of the studied sections. Ammonite zones found in this section are after Guex (1972), Mattei et al. (1967) and Morard (2004). The two sections are
precisely correlated on the basis of integrated ammonite and nannofossil biostratigraphy. Some marker beds (i.e., the Leptolepis bed) are also used to better correlate the two sections.
The first ammonite horizon in SPF corresponds to the Semicelatum Subzone, belonging to the first Toarcian ammonite zone; whilst at TND the first ammonite horizons indicate the
second ammonite zone of the Toarcian. Note that the FO of C. poulnabronei, C. superbus, and D. ignotus are recorded in the same sample in TND, whilst these events are observed in
different samples in SPF. Absolute abundance of calcareous nannofossils (coccoliths plus Schizosphaerella) is compared to wt.% CaCO3. Preservation state of each sample is also
displayed. Absolute abundance of Schizosphaerella is shown separately (empty dots).
wise temperature pyrolysis (300–600 °C), and is expressed in hydro-
carbons (HC) per gram of dry sediment. Although the type of organic
matter is usually defined by mean of elemental analysis, the HI
approximates the H/C atomic ratio, which is determinant for organic-
matter characterization (Tissot and Welte, 1984). The hydrogen index
(HI) is the normalized S2 value (HI = S2 / TOC ⁎ 100) expressed in
milligram HC per gram of TOC. It is characteristic of the type of
organic matter, terrestrial or marine (Tissot and Welte, 1984; Espitalié,
1993). Tmax is the temperature at maximum pyrolytic hydrocarbon
generation expressed in °C. For a given organic-matter type, Tmax
varies as a function of the natural thermal maturity of the organic
matter.
The origin of the organic matter can be evaluated using the
relationship between HI vs. Tmax (Espitalié et al., 1985). According to
these authors, the organic matter can be classified in four types. Types
I and II correspond to fresh organic matter of lacustrine and marine
origin, respectively. Type III is derived from terrestrial higher plants.
Type IV represents highly oxidized oxidised organic matter (Peters,
1986). The HI vs. Tmax plots of Tournadous and Saint-Paul-des-Fonts
are shown in Fig. 5.
3.1.2. Carbon and oxygen stable isotopes
All stable isotope analyses were carried out on bulk carbonates
(31 samples, Tournadous section; Fig. 3). Previous works have proven
the usefulness of bulk rock analysis in pelagic fine-grained and
homogeneous rocks (e.g., Scholle and Arthur, 1980; Anderson and
Arthur, 1983). Carbonate δ13C and δ18O values were measured in a
Finningan Mat delta-S Mass Spectrometer at the Laboratory of Isotope
Geochemistry of the University of Lausanne. Samples were measured
for their carbonate δ13C and δ18O content, following the standard
procedure of Mc Crea (1950), reacted at 50 °C for half an hour. A
fractionation factor of 1.00931 between CaCO3 and H3PO4 was applied
(Swart et al., 1991). All δ13C and δ18O values are reported relative to
VPDB. The standard deviation of the analyses is ±0.05‰ for δ13C,
and ±0.1‰ for δ18O.
3.2. Calcareous nannofossil
Sixty-nine smear slides were prepared for calcareous nannofossil
quantitative analysis (38 from SPF and 31 from TND; Fig. 2). Smear
slides were prepared following the method described by Geisen et al.
(1999). A small amount of powdered rock (~ 30 mg) was dried and
mixed to water (with a basic pH, and over-saturated with respect to
carbonates) in a magnetic stirrer in order to obtain a homogeneous
suspension. The suspension was let settle on a cover slide in a set-
tling device for 24 h. The cover slide was then recovered, dried and
mounted on a microscope slide. Smear slides were studied with a
ZEISS polarizing optical microscope at 1250×. Preservation of calcar-
eous nannofossils was estimated on the basis of the degree of etching
and overgrowth (Roth, 1984), and the fragmentation of specimens.
Three preservation classes were distinguished, namely: 1) poorly
preserved assemblages (P) with heavily etched or heavily overgrown
specimens, commonly fragmented; 2) moderate preservation (M)
presenting slightly etched or slightly overgrown specimens; 3) good
preservation (G) when etching or overgrowth are very limited, or
coccolith structure is pristine.
Between 150 and 400 calcareous nannofossils (both coccoliths and
Schizosphaerella spp., incertae sedis probably a dinoflagellate cyst,
Kälin and Bernoulli, 1984) were counted in a variable number of
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fields of view. In few, very poor samples, a significant number of
nannofossils (100) could not be counted. Absolute abundance of
nannofossil per gram of rock was calculated using the following
formula (after Geisen et al., 1999):
x ¼ ðNTV Þ=ðmTFTSThÞ
where x is the number of calcareous nannofossils per gram of rock;
N is the number of nannofossils counted in a sample; V is the volume
of water used for the dilution in the settling device; m is the weight of
the powder used for the suspension; F is the number of fields of view
in which calcareous nannofossils were counted; S is the surface of a
field of view; h is the height of the water over the cover slide in the
settling device. Species-specific absolute and relative abundance
were also calculated. Coccolith relative abundance was estimated
with respect to the number of coccoliths counted in a slide (Figs. 6 and
7). The samples in which less than 100 coccoliths could be counted
were not taken into consideration for calculation of coccolith
percentage.
3.3. Benthic foraminifers
Thirty-one samples were processed for foraminiferal analyses:
14 samples from the Tournadous section and 17 samples from the
Saint-Paul-des-Fonts section. About 300 g of marl samples were was
submitted to a thermal cracking (the sample was put several times in a
oven and in cold water, alternatively). After the drying and sieving of
residues through 1 mm, 500 μm, 250 μm, 125 μm and 50 μm meshes,
the foraminifers were picked up for all the fractions N125 μm under a
binocular microscope. We however checked also the finest fraction
(50 μm) to check the presence/absence of foraminifera, especially in
the “anoxic” levels. No foraminifers were found in the finest fraction in
these levels. Between 100 and 650 benthic foraminifers per sample
were identified and counted in the size fraction N125 μm. The fora-
miniferal genera classification is based on the work of Loeblich and
Tappan (1988). In the finest fraction (50 μm), only the presence/
absence of the foraminifers was checked.
In the Late Pliensbachian and Early Toarcian, foraminiferal
assemblages were richer at Tournadous than at Saint-Paul-des-
Fonts. In the latter section, only five samples from the Spinatum
Ammonite Zone (Late Pliensbachian) yielded foraminifers, whereas all
the Early Toarcian samples were barren. For this reason, more detailed
analyses have been performed only at Tournadous and data from the
five productive samples in Saint-Paul-des-Fonts are not shown.
In order to evaluate some taphonomic processes (selective
dissolution, hydrodynamic energy, etc.), which could have affected
foraminiferal assemblages, the relative abundance of specimens
fragmented or bearing signs of dissolution, abrasion and micro-boring
was estimated (Fig. 8). The variations in the relative abundance of
fragmented and etched specimens have been compared to those of
robust and biconvex Lenticulina. Experimental evidence shows that
Lenticulina, a hyaline foraminifer, is one of the most resistant taxa to
dissolution (e.g., Nguyen and Speijer, 2007). The relative abundance of
the hyaline dominant genera has been calculated and shown in Fig. 8,
together with the relative abundance of porcellanaceous (mainly
Ophtalmidium) and siliceous agglutinated tests (mainly Glomospirella
and Ammodiscus). The genus richness (number of genera) for each
sample is illustrated as well (Fig. 8).
On the basis of the external test geometry and symmetry, benthic
foraminifers were attributed to 7 morphogroups, mainly following
Bernhard (1986) and Bartolini et al. (1992).
– Morphogroup A: uniserial, elongated and thin specimens belong-
ing to the genera Paralingulina and Ichthyolaria;
– morphogroup B: elongated and spindle-shaped foraminifers, such
as Eoguttulina;
– morphogroup C: uniserial, elongated and cylindrical forms (Proden-
talina, Mesodentalina, Pseudonodosaria, Nodosaria, Marginulina);
– morphogroup D: flat, evolute, planispiral forms (Astacolus, Lenticulina);
– morphogroup E: lenticular, strongly biconvex, involute, planispiral
foraminifers (Lenticulina);
– morphogroup F: discoid test, proloculus followed by undivided
tubular second chamber (Spirillina);
– morphogroup G: trochospiral, conical forms (Epistomina, Reinholdella).
The morphology of the tests of benthic foraminifers is strongly
influenced by life mode (e.g., infauna vs. epifauna, free vs. fixed, etc.) and
by environmental conditions in their habitat (depth, light intensity,
hydrodynamic energy, oxygen availability; Hallock, 1979; Corliss, 1985;
Bernhard, 1986; Corliss and Chen, 1988; Corliss, 1991; Bartolini et al.,
1992; Rey et al., 1994; Jorissen, 1999). Each of these morphogroups
should therefore correspond to peculiar environmental conditions (e.g.,
sea sea-bottom oxygenation, hydrodynamic energy, etc.). For the genus
Lenticulina, the proportion of the morphogroup E vs. the morphogroup D
(E /E +D ⁎ 100) has been calculated and reported in Fig. 8.
On the basis of morphological similarity with recent taxa, we
hypothesized that morphogroups A, B, and C may have corresponded
to infaunal foraminifers, and morphogroups D, E, F, and G to epifaunal
forms (see also Corliss and Chen, 1988; Corliss, 1991). The relative
abundance of infaunal vs. epifaunal morphogroups was calculated; it
is shown in Fig. 3. However, the relationship between test morphology
and microhabitat is complex, and all generalisations have significant
exceptions. Caveats in using morphogroup analysis to infer micro-
habitats and environmental parameters have been exhaustively
discussed by many authors (e.g., Buzas et al., 1993; Jorissen, 1999;
Murray, 2001). For instance, in their statistical study, Buzas et al.
(1993) evaluated that for the taxa they considered, microhabitat
assignments on the basis of morphology were about 75% accurate. We
can thus argue that only major changes in percentages of the
morphogroups are likely significant.
4. Results
4.1. Geochemistry
4.1.1. Carbonate and organic-matter content
Calcium carbonate content (wt.% CaCO3) is relatively low and stable in
the samples from the Upper Pliensbachian both in the Saint-Paul-des-
Fonts section (on average 30%) and Tournadous (20%), with the exception
of few values measured in nodular limestones (Fig. 2). The samples from
the basal Toarcian are nearly depleted in CaCO3 in both sections. A
carbonate recovery is observed from the end of the Exaratum Ammonite
Subzone and, mainly, in the Elegans Ammonite Subzone (on average 45%).
With the exception of a coaly horizon at the Pliensbachian/
Toarcian boundary in the Saint-Paul-des-Fonts section, in which TOC
content attains 58% (Fig. 4), organic content of the studied samples
varies between 0 and 11% and is roughly correlated to lithological
changes. The Upper Pliensbachian marls usually show the lowest
values (b1%), with the exception of few samples, whereas a sharp
increase in TOC content is observed along with the deposition of the
Schistes carton facies (8% on average).
The low Tmax values (average of 425 °C and 426 °C at Saint-Paul-
des-Fonts and Tournadous, respectively) indicate that the organic
matter did not experience high temperatures during burial. A quite
immature organic matter is also documented by Farrimond et al.
(1989) for time-equivalent sediments from North-East France
(Paris Basin). As illustrated in a HI-Tmax diagram (Fig. 5), the studied
samples are immature with respect to oil generation. Consequently,
the type of organic matter can be estimated from pyrolysis data on the
basis of the Hydrogen Index (HI) parameter. According to the wide
range of HI-values recorded (14 to 729 mg HC/g TOC), the organic
matter of the studied samples can be attributed to Types II and III
 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
Fig. 3. Wt% TOC, HI, and Tmax are compared to the carbon and oxygen isotope values measured in the TND section. Empty dots correspond to samples affected by a diagenetic overprint. The shaded area corresponds to the T-OAE. The relative
abundance of infaunal and epifaunal morphogroups indicates sea-bottom oxygenation.

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352 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364

Fig. 4. Wt% TOC, HI, and Tmax values measured in the SPF section. The shaded area corresponds to the T-OAE.

(Fig. 5). Type II corresponds to fresh organic matter of marine origin.
Type III is derived from terrestrial higher plants (Espitalié et al., 1985;
Peters, 1986).
HI is low in the Late Pliensbachian and, similarly to TOC, its
values increase in both sections in the Early Toarcian (Figs. 3 and
4). In the Late Pliensbachian, average values of HI are 35 mg HC/g
TOC at Tournadous, and 130 mg HC/g TOC at Saint-Paul-des-Fonts.
In the Early Toarcian, HI is on average 424 mg HC/g TOC at
Tournadous (maximal values = 729) and 496 mg HC/g TOC at Saint-
Paul-des-Fonts (maximal values = 715). Values higher than 400 mg
HC/g TOC are generally related to marine organic matter (Type II),
dominated by phytoplankton and bacteria with limited proportions
of terrestrial organic matter. Organic matter is of Type III
(terrestrial OM) in the Late Pliensbachian of the two sections,
while marine organic matter (Type II) dominates in the Early
Toarcian (Fig. 5).
In the smear slides corresponding to the samples enriched in
organic matter, pyrite framboids are commonly recorded. In discrete
levels, associated to the framboids are small (1 µm) cubic or
tetrahedral crystals probably corresponding to magnetite (Fe3O4) or
griegite (Fe3S4, precursor of pyrite, FeS2). These can be isolated or
arranged in clusters of about twelve microcrystals.
4.1.2. Carbon and oxygen stable isotopes measured at Tournadous
The carbon isotope values are comprised between −1‰ and +1‰
in the Late Pliensbachian, with the exception of few, very negative
values (−8 and −9‰) recorded in the nodular limestones, diagenetic in
origin, or in the coarse detritic levels bearing HCS structures (Fig. 3). In
these levels, carbon isotope values negatively covary with δ18O. The
very negative carbon isotope values of these samples, and the negative
correlation between carbon and oxygen isotopes are likely the result
of a diagenetic overprint (Raiswell, 1988; Sass et al., 1991; Patterson
 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
Fig. 5. Type of organic matter as derived by the HI vs. pyrolysis Tmax plot. Organic matter is immature in all the studied samples. It is terrestrial in origin in the samples from the
Pliensbachian in both sections but marine in the Toarcian.
and Walter, 1994). The well-known negative excursion of carbon
isotopes (Hesselbo et al., 2000), occurring in different NW Europe
settings in the Exaratum Ammonite Subzone, is probably recorded in the
Tournadous section, although in few (four) samples. In fact, at the base of
the Toarcian (more precisely, just above the Pliensbachian/Toarcian
hiatus), δ13C values decrease to ~−4‰ (Fig. 3). These negative carbon
isotope values correlate to the first increase (up to 10%) of TOC. In the
Saint-Paul-des-Fonts section, the δ13C negative excursion (~−4‰) is also
recorded in very few samples from the Exaratum Ammonite Subzone
(Morard, 2004).
Interestingly, carbon isotope values from one section of the Quercy
Basin (Penne, SW France; Emmanuel et al., 2006), which was very
close to the Causses Basin, are in the same range as in the Tournadous
section. Emmanuel et al. (2006) also record a negative δ13C excursion
of about −4‰ at the base of the Falciferum Ammonite Zone of the
Penne section. In the ANDRA HTM 102 Borehole (NE France, Paris
Basin), a prominent negative excursion of δ13C measured on organic
matter occurs in Lower Toarcian sediments deposited after a hiatus;
the base of the carbon excursion parallels an increase in wt.% TOC
(van Breugel et al., 2006). The record of the Tournadous section in the
Causses Basin is therefore very similar to what is reported from two
other sedimentary basins belonging to the NW European shelf. These
similar records make us think that the isotope values measured in the
Tournadous section are primary, and that they represent the
expression of the Early Toarcian anoxic event, albeit high TOC values
persisted in the Causses Basin until the end of the Early Toarcian.
The oxygen isotope data (bulk carbonates) show average values
of −4.25‰ in the samples from the Upper Pliensbachian of the
Tournadous section, and −5.5‰ for the Lower Toarcian samples. These
very negative values could be seen as the result of diagenetic overprint
rather than in terms of palaeotemperature. Alternatively to the
diagenetic hypothesis, the very negative values of oxygen isotopes
in the Causses Basin may be due to a low-salinity superficial water-
body. Oxygen isotope values in the same range as in the Causses Basin
are reported from the Quercy Basin (SW France; Emmanuel et al.,
2006) and from the south-west German Basin for the same time
353
interval (Röhl et al., 2001). These authors interpret such negative
values in terms of important fresh-water input from rivers surround-
ing the Quercy and south-west German Basins, respectively. Similarly,
the Causses Basin was bounded by emerged lands. It likely received
significant riverine inputs, mainly during the Early Toarcian when
an enhanced hydrological cycle is inferred on the basis of osmium
isotopes (Cohen et al., 2004).
If we assume that the fresh-water input produced a fairly constant
shift towards more negative oxygen values for all the samples, the
general trend of the curve in Fig. 3 is consistent with data presented in
the palaeotemperature dealing with palaeotemperature fluctuations.
Indeed, various authors (McArthur et al., 2000; Röhl et al., 2001;
Bailey et al., 2003; Rosales et al., 2004; Suan et al., 2008a) have
inferred a temperature minimum in the Late Pliensbachian, followed
by a warming trend in the Early Toarcian, on the basis of oxygen
isotope analyses on bulk rock, or on biogenic carbonates of belemnite
rostra and brachiopod shells.
4.2. Calcareous nannofossils
4.2.1. Preservation
In (palaeo)environmental studies, calcareous nannofossil preser-
vation has to be carefully checked in order to avoid misinterpretations
of assemblage compositions. In the Upper Pliensbachian sediments,
calcareous nannofossils are generally well-preserved at Tournadous
(Fig. 6) and moderately preserved at Saint-Paul-des-Fonts (Fig. 7). In
general etching, although limited, is more commonly observed than
overgrowth. As the samples are let settle for 24 h in water
oversaturated with respect to carbonates, calcite re-precipitation
and overgrowth on calcareous nannofossils may occur, especially
during the drying of slides. This is the reason why the samples in
which overgrowth was observed have been re-analysed using simple
smear-slide preparation. Because the quantity of water used for smear
slides is very limited, this technique prevents nannofossil overgrowth
during sample preparation. The two sets of samples were then
compared, and no difference was observed in nannofossil overgrowth.
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S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
Fig. 6. Absolute and relative abundance of the most commonly recorded nannofossil taxa in the Tournadous section. Ex. = Exaratum Ammonite Subzone. The shaded area corresponds to the T-OAE. The various taxa show peaks in abundance in
different stratigraphic intervals with respect to the T-OAE.
 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
Fig. 7. Absolute and relative abundance of the most commonly recorded nannofossil taxa in the Saint-Paul-des-Fonts section. The shaded area corresponds to the T-OAE. Albeit the proportion of some taxa is different with respect to TND (see
Fig. 6), a similar trend in nannofossil distribution is observed.

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S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
Fig. 8. Only 10 of the 14 studied samples from the Tournadous section yielded benthic foraminifers. From left to right: relative abundance of fragmented foraminifers and relative abundance of specimens bearing evidence of abrasion, dissolution,
micro-boring; relative abundance of Lenticulina E and Lenticulina D morphogroups; relative abundance of genera belonging to the different morphogroups. See the text for further explanation. The shaded area corresponds to the T-OAE.
 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
The nodular, carbonate-rich beds of the Late Pliensbachian (probably
diagenetic in origin) contain moderately or badly preserved calcar-
eous nannofossils; fragmentation of schizospheres is also observed
in these levels. The clay-rich base of the Schistes carton (Schistes
Papyracés) is characterized in the two sections by poorly to
moderately preserved nannofossils. Preservation improves along
with the increase in calcium carbonate content within the Serpenti-
num/Falciferum Ammonite Zone (Figs. 6 and 7). As the overall effects
of etching and overgrowth are limited, and because of the presence of
coccoliths prone to dissolution (such as specimens of the Biscutaceae
or Calyculus) all along the studied interval, we can reasonably consider
that the assemblage composition of the Tournadous and Saint-Paul-
des-Fonts samples is rather pristine.
4.2.2. Biohorizons in the studied sections
At Tournadous (Fig. 2), Lotharingius sigillatus and Crepidolithus
cavus (=C. impontus of Bown and Cooper, 1998) are recorded from
the base of the section, 2.62 m below the Pliensbachian/Toarcian
boundary as defined by ammonites. Calyculus spp. is recorded
from 0.38 m, very close to the base of the studied section. We do
not consider therefore this datum as a real first occurrence (FO).
Lotharingius crucicentralis and Lotharingius aff. L. velatus first occur at
1.33 m and 1.54 m, respectively, within the Spinatum Ammonite Zone
(Late Pliensbachian). The FO of Biscutum aff. B. intermedium is at
1.98 m. At Saint-Paul-des-Fonts (Fig. 2), L. sigillatus, L. crucicentralis,
L. aff. velatus, C. cavus, and B. aff. intermedium are recorded from the
base of the section, 2.66 m below the Pliensbachian/Toarcian
boundary. Lotharingius aff. L. velatus, very similar to L. velatus but
with a thinner ring, has been already reported by Veiga de Oliveira
et al. (2005) from the latest Pliensbachian of the Lusitanian Basin
(Peniche section).
The majority of the stratigraphic interval corresponding to the
Tenuicostatum Ammonite Zone is lacking in the entire Causses Basin
(Trümpy, 1983; Guex et al., 2001; Morard et al., 2003). However, in the
Saint-Paul-des-Fonts section a horizon is recorded at 2.6 m that is
enriched in ammonite specimens characteristic of the upper part of the
Semicelatum Subzone (Morard, 2004). At Tournadous, the hiatus
seems to be more important than at Saint-Paul-des-Fonts because the
base of the Schistes carton is dated as Serpentinum/Falciferum
Ammonite Zone (Morard, 2004). The FOs of Carinolithus superbus,
C. poulnabronei, and Discorhabdus ignotus are recorded in the same
sample at Tournadous, whilst at Saint-Paul-des-Fonts D. ignotus is
recorded some 20 cm above Carinolithus. Accordingly, calcareous
nannofossil data also suggest a different duration of the hiatus in the
two sections. Mitrolithus jansae has not been observed at Tournadous,
and only rare and sporadic specimens have been observed at Saint-
Paul-des-Fonts, which was situated in a more distal position within the
Causses Basin. The last occurrence (LO) of this taxon is recorded
at 6.9 m (Fig. 2). On the basis of calcareous nannofossil record, it is
possible to recognize in the two sections the nannofossil Subzone NJ5b
C. cavus (=C. impontus), as defined for the NW Europe by Bown and
Cooper (1998). The base of the overlaying calcareous nannofossil Zone
NJ6 C. superbus very probably lays within the sedimentary hiatus.
4.2.3. Calcareous nannofossil absolute abundance
On average, nannofossil abundance (sum of coccoliths and
nannoliths) is higher in the Saint-Paul-des-Fonts section (352E6 spec-
imens per gram of rock) than at Tournadous (287E6 specimens per
gram of rock; Fig. 2). Coccoliths are dominant over the nannolith
Schizosphaerella (graphs with empty dots in Fig. 2) in both sections.
Abundance values are quite constant and relatively low in the Late
Pliensbachian of Tournadous, where wt.% CaCO3 is also low (b20%).
Absolute abundances are relatively high in both sections in the latest
part of the Pliensbachian, Hawskerense Ammonite Subzone, where
wt.% CaCO3 varies between 30% and 80%. Very low abundance values
or barren samples are recorded in the basal part of the Toarcian
357
(Schistes Papyracés), where wt.% CaCO3 is also extremely low (b5%), or
in the nodular, diagenetic limestone beds. We do not recognize in the
studied sections the “schizospherellid crisis” inferred for the same
time interval by Erba (2004) and Tremolada et al. (2005). In fact, not
only Schizosphaerella but also coccolith abundance is drastically
reduced during the T-OAE. The rest of the Early Toarcian shows
increasing calcareous nannofossil abundance up to the highest values
(2200E6 specimens per gram of rock) measured in the Saint-Paul-des-
Fonts section. In this interval, carbonate values also increase in each
section (on average, CaCO3 is ~45%).
4.2.4. Assemblage changes through time
In the Tournadous section, calcareous nannofossil assemblages are
largely dominated by coccoliths, while Schizosphaerella spp. accounts
on average for less than 12% of total assemblages (Fig. 2). Relatively
high proportions of this taxon are recorded only in nodular,
carbonate-rich beds that bear poor assemblages with rare coccoliths.
In Fig. 6, absolute and relative abundance of the most commonly
recorded coccoliths show the same general trend. The fluctuations in
relative abundance are therefore not related to a closed sum effect,
with the exception of few samples (i.e., at 3.4 m). Some taxa, such as
Bussonius (mainly B. prinsii with subordinated B. leufuensis), L. barozii,
T. patulus and P. liasicus, have relative abundances showing high
values at the base of the section, in the Spinatum Ammonite Zone.
Some other taxa (Crucirhabdus and S. novum + S. finchii) are relatively
abundant from the late Spinatum Zone to the base of the Elegans
Subzone. It must be observed, however, that between these two zones
there is a gap including at least all the Tenuicostatum Zone. It is
interesting to note that in the Late Pliensbachian under-calcified
coccoliths of Bussonius, Lotharingius and Similiscutum are commonly
recorded. A peak in absolute and relative abundance of Calyculus and
Orthogonoides is observed at the base of the Elegans Zone. This last
form is an incertae sedis that morphologically resembles to ascidia
spicules of the living didemnidae (see Kott, 2005). The species
dominating the assemblage in the upper part of the section (Elegans
Subzone) are Similiscutum spp., L. hauffii, C. crassus and C. cavus.
In the Saint-Paul-des-Fonts section the trends of calcareous
nannofossil assemblages are similar to those observed at Tournadous.
The abundance of Schizosphaerella (Fig. 2) is lower than at Tournadous.
As the Late Pliensbachian interval at Saint-Paul-des-Fonts is shorter
in terms of duration than that studied at Tournadous, Bussonius,
L. barozii, T. patulus, P. liasicus, Crucirhabdus and S. novum +S. finchii are
observed to peak in the same ammonite zone. In the interval where
calcareous nannofossil absolute abundance is very low, Calyculus and
Orthogonoides display a peak (Exaratum to Elegans Ammonite Sub-
zones) whereas, in the rest of the Early Toarcian, assemblages are
dominated by Similiscutum spp., L. hauffii, C. crassus and C. cavus. It is
interesting to note that Crepidolithus crassus, which is very abundant in
the Elegans Ammonite Subzone in both sections, is the largest coccolith
in Lower Toarcian assemblages. Although entire coccospheres have not
been recorded, some coccolith measurements performed in this work
allow us to estimate an average volume of 163 µm3 for the specimens
of the Causses Basin, which compared to modern coccolithophore
species is quite huge. The main differences between the two
sections are related to the percentage of various taxa (see for example
L. barozii; Figs. 6 and 7) that can be more or less abundant in proximal
(Tournadous) with respect to distal settings (Saint-Paul-des-Fonts).
4.3. Benthic foraminifers
In the Late Pliensbachian and Early Toarcian interval of the
Tournadous section, the benthic foraminiferal assemblages are largely
dominated (98–99%) by hyaline taxa (mainly calcitic Lagenida and
aragonitic Robertinida). Porcellanaceous and agglutinated taxa are
very rare (1–2%) in the studied samples (Fig. 8). Foraminifers are
generally moderately to poorly preserved. Most of the tests are filled
358 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
with secondary calcite, recrystallised, and a high percentage of
specimens are fragmented (from 10 to 20% in the Upper Pliensbachian
samples; Fig. 8). In the uppermost part of the Pliensbachian and in the
Lower Toarcian samples, the original tests are often replaced by pyrite
(for example, from the sample TND 21 upwards in the Tournadous
section). Although we cannot exclude a preservation control on the
foraminifer assemblage composition, some patterns of faunal assem-
blages seem to correspond to primary environmental signals, such as
variations in hydrodynamic energy, flux of organic matter, oxygen
level, etc.
4.3.1. Hydrodynamism vs. dissolution
In the Tournadous section (Fig. 8), the relative abundance curve
of the fragmented specimens is roughly parallel to that of the robust,
biconvex, and involute Lenticulina (morphogroup E). From samples
TND 9 to TND 29, the high relative abundance of both fragmented
specimens and Lenticulina morphogroup E may be interpreted as
the result of a selective dissolution. However, high abundance of
Lenticulina morphogroup E and of fragmented specimens do not
coincide with the increase in siliceous agglutinated taxa, suggesting
that foraminiferal assemblages still preserve primary, environmental
information. As an alternative explanation, the increase in Lenticulina
E together with fragmented specimens may be interpreted as the
result of important winnowing. The increase in signs of abrasion on
the Lenticulina tests (Fig. 8), especially in the first Toarcian sample
(TND 29), supports the hypothesis of an important winnowing.
An exception is represented by the sample TND 37, where a
peak of Lenticulina E corresponds to an increase in dissolution of the
Lenticulina tests, but in this case a decrease of fragmented specimens
was observed. In this sample, the dissolution has clearly a major
impact on the assemblage composition. Interestingly, this peak of
Lenticulina E with signs of dissolution is associated with abundant
(20%) Reinholdella, an aragonitic taxon that should be very susceptible
to dissolution. We may explain this paradox assemblage as the result
of “time averaging” (Martin, 1999). Lenticulina and Reinholdella were
probably not co-existing, but they likely correspond to a succession of
different assemblages, adapted to peculiar environmental conditions.
These assemblages are recorded in an artificial mixing, due to the
extremely low accumulation rate and condensation. Robust, involute
and biconvex Lenticulina (morphogroup E) were likely better adapted
to increased energy with respect to the more evolute, flat Lenticulina
and Astacolus (morphogroup D; see also Larsen and Drooger, 1977;
Hallock, 1979; Rey et al., 1994).
The increased proportion of morphogroup E with respect to
morphogroup D (E / E + D × 100) in the samples TND 1 to TND 25
(Fig. 8) seems also be the result of a high environmental energy,
probably related to the regressive trend of the end-Pliensbachian.
This general trend of increased energy is interrupted by a decrease of
energy in the sample TND 13. After the emersion leading to the
Pliensbachian/Toarcian hiatus (Morard et al., 2003), the Lower
Toarcian transgression produced shallow-sea environments in
which storm events occurred, as testified by the levels bearing
hummocky cross-stratifications. High energy and shallow-water
conditions are also suggested by the highest proportion of the
morphogroup E with respect to morphogroup D in the sample TND
29 (Fig. 8). In this sample, a small peak (1.4%) of Ophtalmidium and
the presence of rare Nubecularia (fixed specimens) may indicate
shallow-water conditions, extreme condensation, and the temporary
development of firm grounds. Stratigraphically upwards (TND 37
and 41), the proportion of morphogroup E vs. morphogroup D
decreases (Fig. 8), probably mirroring a decrease in environmental
energy and a deepening trend.
4.3.2. Organic Organic-matter flux and sea-bottom oxygenation
Besides the control of hydrodynamic energy and of sea-level
changes on foraminiferal assemblages, organic-matter flux and
oxygenation at the sea bottom are important factors controlling
benthic life. The parameters of bottom-water oxygenation and organic
flux (food availability) are closely interrelated, and it is often extremely
difficult to distinguish their respective influences (Jorissen, 1999). In
the samples TND 1, 5 and 9, foraminiferal assemblages are char-
acterized by abundant, highly sculptured Marginulina and by
finely ornamented Ichthyolaria. Both taxa can attain a large size
(250–1000 μm). Large Lenticulina (135–625 μm) are also recorded in
the same levels (Fig. 8). Morphogroups A, C, and D are relatively
abundant in this interval (Fig. 8). Foraminiferal assemblage is
dominated by infauna in the samples TND 1 and 5, whereas infauna
is more or less equivalent to epifauna in TND 9 (Fig. 3). These data may
be indicative of conditions favourable to benthic life development, a
quite stable and oxidizing oxidising environment. However, an
environmental stress was probably induced by a progressive increase
in hydrodynamic energy from sample TND 1 to TND 9, as discussed
above. The reduction in the number of genera in the sample TND 9
could be, at least in part, the result of this increase in energy.
The sample TND 13 is characterized by a peak in the relative
abundance of Lenticulina morphogroup D and of Reinholdella, and by a
marked decrease in relative abundance of Ichtyolaria and Marginulina
(Fig. 8). Interestingly, this change in the assemblage composition is
correlated with a little peak of TOC (0.90%) and of HI (140), as shown in
Fig. 3. Reinholdella and Lenticulina morphogroup D become dominant
in the Early Toarcian, in the interval characterized by levels enriched
in organic matter (TND 37 and 41), and probably corresponding to
dysaerobic conditions at the sea bottom. The assemblage of the sample
TND 13 likely mirrors an increase in the organic-matter flux (Fig. 8). In
spite of the increase in the organic-matter flux, sea bottom was (at least
temporarily) well oxygenated, as indicated by the highest genus
richness observed in this sample (Fig. 8), and by the comparable
abundance of infauna and epifauna (Fig. 3). Moreover, almost all the
foraminiferal morphogroups are present in this sample (Fig. 8). Cool
water temperatures in this interval are probably responsible for a
higher concentration of dissolved oxygen in bottom waters. Oxidising
bottom waters likely favoured organic-matter remineralization.
In the upper part of the Spinatum Ammonite Zone, below the
sedimentary hiatus (samples TND 21 and TND 25), the faunal
composition changed as shown by the important increase in relative
abundance of Paralingulina (20–25%), associated with high propor-
tions of Marginulina (18–25%), and a marked decrease in relative
abundance of Ichthyolaria and Lenticulina morphogroup D. We
observed in these samples a general reduction in size of benthic
foraminifers, and especially of Marginulina (b250 μm). It is noteworthy
that Ichthyolaria and Paralingulina are roughly anti-correlated
throughout the section (Fig. 8).
In the Umbria–Marche Basin (central Italy; South-West Tethys),
Paralingulina has been recorded dominant in the Lower Toarcian
black shales, where wt.% TOC attains its highest values (1.4–2.2%;
Bartolini et al., 1992). The increase in relative abundance of Paralin-
gulina at Tournadous may be related to an increase in nutrients and
organic-matter flux, but the sea-bottom conditions still remain
oxidising as indicated by the high genus richness. According to the
model of Jorissen et al. (1995), Paralingulina tenera could be
considered as a deep infaunal taxon, favoured by a high flux of
organic matter (eutrophisation), and tolerant to dysoxic conditions. In
the Upper Pliensbachian samples of Tournadous, the increase in
nutrients is associated with a regressive phase and a probable cooling
trend, as indicated by the δ18O curve (Fig. 3). The slight increase in
relative abundance of siliceous agglutinated Glomospirella in the
sample TND 25, just below the hiatus, may be related with this cooling
trend or to a slight variation in ambient pH (Nocchi and Bartolini,
1994).
The first sample of the Early Toarcian above the hiatus (TND 29) is
characterized by a slight decrease in the genus richness (Fig. 8). The
faunal composition is characterized by an increase in relative
 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
abundance of Lenticulina morphogroup E and by the presence of
porcellanaceous Ophtalmidium. The relative abundance of small-sized
Paralingulina and Marginulina (b250 μm) is still high with respect to
the samples in the upper part of the Spinatum Ammonite Zone. The
sample TND 29 corresponds to a marked increase in organic matter
(4.27%; Fig. 3). In the overlying samples (TND 37 and TND 41), a
substantial change in the assemblage composition is observed,
namely a dramatic decrease of the genus richness (Fig. 8). Epifauna
is dominant over infauna (Fig. 3), foraminifers are significantly small
and non-ornamented, the diversity is reduced and the morphogroup
G (mainly Reinholdella) becomes progressively dominant (Fig. 8). The
samples TND 37 and TND 41 are relatively enriched in organic matter
(wt.% TOC is 1.95 and 1.88, respectively), and they are in an interval
characterized by very high TOC values (6–8%). We interpret the
Reinholdella as opportunistic forms, tolerant to hypoxic conditions
(see also Copestake and Johnson, 1981). Reinholdella was probably
an opportunistic phytodetritus feeder, surface-dwelling species,
which could benefit of short periods of bottom-water re-oxygenation.
In the samples TND 29 and TND 37, the high values of wt.% TOC and
the co-existence of taxa indicating oxidising environments, such as
Lenticulina morphogroup E, with low-oxygen tolerant taxa, such as
Paralingulina and Reinholdella, may be the result of “time averaging”,
as discussed previously. In this interval, the faunal composition pro-
bably indicates alternating oxidising and hypoxic conditions. Alter-
natively dysoxic to anoxic sediments are likely to have favoured
carbonate dissolution when re-oxygenation occurs (Green et al.,
1993). This could explain the presence of robust Lenticulina tests with
clear trace of dissolution, as the remains of selective dissolution
processes during re-oxygenated intervals.
The general trend of foraminiferal assemblage at Tournadous
indicates that the environmental conditions deteriorated in terms of
sea-bottom oxygenation passing from the Late Pliensbachian to the
Early Toarcian, until a complete disappearance of benthic fauna from
4.45 m upwards. Foraminifers are absent also in the finest fraction
(50 μm). This level probably corresponds to the development of more
permanent sea-bottom anoxia. In the Saint-Paul-des-Fonts section, all
the analysed Lower Toarcian samples are barren in benthic forami-
nifers, probably indicating that in this deeper area of the basin the sea-
bottom anoxia developed earlier than in the shallower Tournadous
area.
5. Discussion
5.1. Palaeoenvironmental conditions prior to the T-OAE
In spite of little differences in the abundance of some calcareous
nannofossils recorded in the proximal (Tournadous section) with
respect to the distal (Saint-Paul-des-Fonts section) settings of the
Causses Basin, some common trend can be traced. Some taxa, such
as P. liasicus, Bussonius spp., and L. barozii, have relative and abso-
lute abundance peaks in the Late Pliensbachian of both sections
(Figs. 6 and 7). These taxa are usually recorded in higher proportions
along the northern margin of the Tethys than in sections at low
palaeolatitudes (Bucefalo Palliani et al., 2002; Mattioli et al., in press).
Their latitudinal distribution can be interpreted in terms of sea-
surface temperature, and their abundance in the Late Pliensbachian
may therefore indicate the development of temperate water-masses
at relatively low palaeolatitudes. This interpretation is consistent with
the general trend of cooling recorded from the Late Pliensbachian
on the basis of oxygen isotopes or Mg/Ca ratio measured on the
carbonates of belemnites (McArthur et al., 2000; Bailey et al., 2003;
Rosales et al., 2004; van de Schootbrugge et al., 2005a,b) and of oxygen
isotopes of brachiopod shells (Suan et al., 2008a). This interval is
also characterized by the occurrence of meso-eutrophic nannofossil
taxa (namely, S. novum and S. finchii; Bucefalo Palliani and Mattioli,
1995; Mattioli and Pittet, 2004; Tremolada et al., 2005; Mattioli et al.,
359
in press). Surface waters in the Causses Basin seem therefore to be cool
and rich in nutrients in the Late Pliensbachian (Fig. 9a). Nutrients were
also available at sea bottom, as indicated by relatively high propor-
tions of Paralingulina. This taxon was in fact part of the deep infauna,
and was favoured by a high organic flux (Bartolini et al., 1992). The
water column at that time was well oxygenated as testified by low
organic-matter preservation in sediments, and by the abundant and
diverse benthic foraminifer assemblages (Fig. 9).
A clear regressive trend is documented in the Late Pliensbachian of
the Causses Basin (Fig. 9b), culminating with emersion at the end-
Pliensbachian/base of Toarcian (Guex et al., 2001; Morard et al., 2003).
Similarly, in the Lusitanian Basin (Portugal) an important regression is
inferred for the end-Pliensbachian on the basis of facies analysis
(Duarte et al., 2004, 2007). A regressive trend and an increase in
environmental energy are inferred for the Tournadous section on
the basis of foraminiferal assemblage (Fig. 8). Biconvex, quite globular
Lenticulina morphogroup E are in fact observed that, due to sea-
bottom winnowing, are often abraded. The record of low temperatures
in a period of global sea-level regression (Hallam, 2001; Hardenbol
et al., 1998) leading to emersion and hiatuses in various NW Europe
settings (i.e., South Burgundy area, Elmi and Rulleau, 1993; Causses
Basin, Guex et al., 2001; Provence area, Floquet et al., 2003; Paris Basin,
van Breugel et al., 2006; sill between the Paris and Aquitanian Basins,
Galbrun et al., 1994; Courtinat et al., 2007), is consistent with the
hypothesis of ice-caps formation (Guex et al., 2001; Morard et al.,
2003). The occurrence of glendonites and dropstones at high
palaeolatitudes in the Late Pliensbachian (Price, 1999) further
supports this hypothesis.
5.2. Palaeoenvironmental conditions during the T-OAE
A warming trend characterizes the Early Toarcian (McArthur et al.,
2000; Bailey et al., 2003; Rosales et al., 2004; van de Schootbrugge
et al., 2005a,b; Suan et al., 2008a), that it is probably related to an
increase in atmospheric pCO2 (Hesselbo et al., 2000; Beerling et al.,
2002; Suan et al., 2008a), although it is not excluded that temperature
fluctuations were modulated by orbital cycles (Suan et al., 2008b).
This warming trend occurred at the same time as a global, 3rd order
transgression (Hardenbol et al., 1998; Hallam, 2001), although the
precise relationship between warming and sea-level changes has not
been ascertained yet. The transgression is recorded diachronously in
the Causses area, according to the morphology of the basin. At Saint-
Paul-des-Fonts (more distal) a level enriched in ammonite specimens
indicating the Semicelatum Ammonite Subzone (corresponding to a
part of the 1st ammonite zone of the Early Toarcian) is recorded
after the hiatus (Fig. 2) (Morard, 2004). Conversely, at Tournadous
(more proximal) the first ammonite horizons are indicative of the
second ammonite zone of the Toarcian, the Exaratum Ammonite
Subzone (Fig. 2). Calcareous nannofossil biostratigraphy further
confirms the diachroneity in the record of the transgression, as it
can be seen in Fig. 2 with the different occurrence of C. poulnabronei,
C. superbus and D. ignotus in the two sections. Although the Upper
Pliensbachian/Lower Toarcian hiatus had a different temporal exten-
sion within the basin, the T-OAE is recorded in the two sections.
In many sections of the western Tethys, the T-OAE is not only
associated to an enrichment in organic matter in the sediments, but
also to a negative carbon isotope excursion occurring in the Exaratum
Ammonite Zone (Hesselbo et al., 2000). At Tournadous (this work) and
Saint-Paul-des-Fonts (Morard, 2004), the T-OAE corresponds to the
interval in which very negative δ13C values (~−4‰) and a first increase
in TOC are recorded (shaded area in Figs. 3 and 4). TOC values remain
high in the two sections for the rest of the Early Toarcian. However,
it must be noted that high TOC values are commonly recorded in
sediments overlying the T-OAE, mainly in sections located along the
N-Tethyan margin (Baudin, 1989; see also the Dotternhausen section
in SW Germany, Röhl et al., 2001, and the HTM-102 Borehole in NE
360 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364

Fig. 9. Cartoon showing sea level and oxygenation evolution along a N–S transect in the Causses Basin. (a) During the Late Pliensbachian, the entire water column was well
oxygenated, nutrients were available both at sea bottom and in surface waters. (b) Between the latest Pliensbachian and the earliest Toarcian, a low sea level led to emersion of many
localities of the Causses Basin. (c) The following trend to increasing temperatures might have led to a sea-level rise, a stratification for density and, finally, to the development of
anoxia within the Causses Basin. Benthic fauna is absent in the studied sections, and nannofossil assemblages are dominated by taxa adapted to stressing conditions (see text for
further explanations). (d) With the ongoing sea-level rise and the development of storms, water stratification and anoxia were progressively reduced. Surface water environments
were re-colonised by an abundant and diverse nannoplankton community. Benthic foraminifers developed again at the basin margins, whilst in the central parts of the basin sea
bottom was still anoxic.

France, van Breugel et al., 2006). Within some sedimentary basins,
stratification of the water column and sea-bottom anoxia persisted
long-time after the T-OAE, at least until the end of the Early Toarcian
or even in the Middle Toarcian (Baudin, 1989; Baudin et al., 1990).
Apparently, anoxic conditions persisted in spite of the fact that storm
events developed within the Causses basin, as demonstrated by storm
deposits showing HCS. These events probably produced short-lived
re-oxygenation at the sea bottom. Benthic foraminifers in fact indicate
alternating dysoxic–oxic conditions at the sea bottom in the first
Toarcian deposits of Tournadous, but environmental conditions
 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
rapidly deteriorate in terms of sea-bottom oxygenation during the T-
OAE until a complete disappearance of benthic fauna (Fig. 5). At Saint-
Paul-des-Fonts, benthic fauna is completely absent in the lower
Toarcian samples. This datum may indicate that sea-bottom anoxia
developed earlier in the deeper parts of the Causses Basin and
eventually migrated towards its margins (Fig. 9).
Different authors have indicated that the base of the negative
isotope excursion roughly coincides with the base of the C. superbus
nannofossil Zone (Bailey et al., 2003; Mattioli and Pittet, 2004;
Mattioli et al., 2004; Tremolada et al., 2005; Mailliot et al., 2006; van
Breugel et al., 2006). The same record is observed in this work.
The lowest absolute abundances of calcareous nannofossils are
recorded in the Exaratum Ammonite Subzone in both studied
sections. Although nannofossil preservation is moderate or poor in
the samples from the Exaratum Ammonite Subzone, these very low
abundances are not interpreted here as being related to nannofossil
dissolution in the water column or within the sediment. In fact,
solution-susceptible coccoliths (like Calyculus spp., or the small and
delicate Crucirhabdus spp.) show some abundance peaks in this
interval. Furthermore, this pattern is not uniquely observed in the
Causses Basin, a similar drastic decrease in abundance is observed in
various settings of the western Tethys (Mattioli et al., 2004; Erba,
2004; Tremolada et al., 2005; Mattioli et al., in press).
Finally, similarly to the record of many other Tethyan settings
(Mattioli et al., in press), during the T-OAE a peak in Calyculus spp. is
observed in this work concomitant with very low absolute abundance of
nannofossils. In both sections, high relative and absolute abundances
of Calyculus spp. are recorded along with a peak in Orthogonoides
hamiltoniae (shaded area in Figs. 6 and 7). Calyculus spp. is considered as
inhabiting the uppermost surface waters, and being adapted to extreme
surface water conditions, in terms of low salinity and water column
stratification (Mattioli et al., in press) Low salinity in the surface waters
of the Causses Basin is consistent with the anomalously negative oxygen
isotope values measured in the Tournadous samples.
Although previous works (Mattioli et al., 2004; Erba, 2004;
Tremolada et al., 2005) interpret the drastic decrease in abundance
of calcareous nannofossils during the T-OAE as a marine bio-
calcification crisis directly induced by high atmospheric pCO2,
the results of this work rather validate the hypothesis of Mattioli
et al. (in press). The latter authors consider the crisis of calcareous
nannoplankton and the dominance of tolerant taxa during the T-OAE
(mainly Calyculus spp. and Orthogonoides hamiltoniae), as an indirect
consequence of high atmospheric CO2. In fact, climatic effects of
increased CO2 are an enhancement of the hydrological cycle (Cohen
et al., 2004; Hesselbo et al., 2007), increase of fresh-water inputs from
continents to the seas (Röhl et al., 2001), and an important lowering of
salinity in surface waters of epicontinental basins surrounding the
Tethys (McArthur et al., 2000; Röhl et al., 2001; van de Schootbrugge
et al., 2005a; Emmanuel et al., 2006). Besides the environmental stress
induced by a low-saline surface waterbody, the peaks in Calyculus spp.
and Orthogonoides spp. in a period of very low proliferation of other
nannoplankton taxa can be also related to the presence of reduced
nitrates within the photic zone. Indeed, a positive shift of δ15N in black
shales of the T-OAE (Jenkyns et al., 2001) is interpreted in terms of
bacterial denitrification within the water column and diffusion of NH+4.
In these conditions, the majority of coccolithophorids were probably
overwhelmed by other phytoplankton groups (Bucefalo Palliani et al.,
2002; van de Schootbrugge et al., 2005a,b).
In the interval enriched in organic matter, pyrite framboids are
commonly recorded. The cubic or tetrahedral crystals associated to the
framboids probably correspond to magnetite or griegite. If these
magnetite or griegite crystals are primary, they could have been
produced by biomineralisation of magnetotactic bacteria (e.g.,
Aquaspirillum magnetotacticum, see Frankel and Blakemore, 1984),
living in marine environments at the transition zone between
oxidising and reducing conditions (Bazylinski and Frankel, 2000).
361
These bacteria use the magnetic properties of magnetite or griegite
under dysoxic and anoxic conditions, respectively, to be oriented with
respect to oxidising zones within the water column (Kopp, 2001). In
the majority of magnetotactic bacteria, these crystals form chains or
clusters (Bazylinski and Frankel, 2000). The record of such clusters in
the Serpentinum/Falciferum Zones of the studied sections may testify
for the occurrence of reducing conditions within the water column
(Fig. 9c and d). In Lower Toarcian black shales from different Tethyan
settings, anoxia within the photic zone has been inferred on the basis
of the presence of biomarkers derived from photosynthesing bacteria
living under sulphide, anoxic conditions (Schouten et al., 2000;
Pancost et al., 2004; Schwark and Frimmel, 2004; van Breugel et al.,
2006). If reducing conditions attained per ascensum the base of
the photic zone in the Causses Basin, deep-dweller coccoliths (like
C. crassus; Bour et al., 2007; Mattioli et al., in press) could not develop
during the T-OAE (Fig. 9c). This is probably the reason why the lowest
abundance of Crepidolithus spp. is recorded in this interval.
5.3. Palaeoenvironmental conditions after the T-OAE
Absolute nannofossil abundances attain very high values in the
interval above the T-OAE (Fig. 9d). This is a common pattern in western
Tethys (Bucefalo Palliani et al., 2002; Mattioli and Pittet, 2004; Mattioli
et al., 2004; Tremolada et al., 2005; Mattioli et al., in press). This pattern
testifies for a recovery of environmental conditions within the photic
zone, and an improvement of trophic conditions. Stratification for
density was probably removed thanks to the storm action and,
although nutrients were available all the time as the Causses Basin
was surrounded by emerged lands (representing source areas), the re-
occurring mixing within the water column favoured a better re-cycling
of nutritive elements. Nutrients were also available at the sea bottom,
as indicated by the high proportions in this time interval of the benthic
foraminifer Reinholdella (Tournadous section). This taxon is commonly
interpreted as an opportunist, sediment surface-dweller, which likely
proliferated during short-lived periods of sea-bottom re-oxygenation.
After the T-OAE, the recolonisation by nannoplankton of the deep
photic zone occurred due to the removal of anoxia, according to the
high relative and absolute abundance of the deep-dweller Crepido-
lithus crassus (Figs. 6 and 7). Anoxia persisted however in the deepest
parts of the Causses Basin, because benthic foraminifers did not
recover in the Saint-Paul-des-Fonts section (Fig. 9d).
There is a fairly good parallelism between the nannofossil absolute
abundance increase, the dominance in the assemblage of Crepidolithus
spp., and the highest values of TOC and HI (compare Figs. 6 and 7 with
Figs. 4 and 5). The nature of the organic matter is essentially marine
in this interval, and primary productivity seems to be elevated. High
primary productivity is also inferred on the basis of important rela-
tive and absolute abundances of meso-eutrophic coccolith taxa
(mainly Similiscutum finchii and S. novum; Bucefalo Palliani et al.,
2002; Mattioli and Pittet, 2004; Tremolada et al., 2005; Mattioli et al.,
in press). Although an interpretation of the carbon isotope trend
during the Early Toarcian is behind the scope of this work, a high
primary productivity starting from the Elegans Ammonite Subzone
would be consistent with the positive excursion of δ13C. A high
primary production leads to a decrease in the 12C reservoir of surface
waters because of photosynthesis, resulting in a positive excursion of
δ13C of marine carbonates (Anderson et Arthur, 1983). We postulate
that nannoplankton was a major contributor to marine productivity at
the end of the Early Toarcian, and that Crepidolithus crassus, the largest
coccolith in Lower Toarcian assemblages, could have significantly
contributed to biomass production.
6. Summary and conclusions
In geological times characterized by important organic-matter
accumulation, like during OAEs, it is difficult to assess the contribution
362 S. Mailliot et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 346–364
of an enhanced primary production and, respectively, bottom-water
reducing conditions enabling the preservation of organic matter
in sediments. In the present paper, an integrated study (calcareous
nannofossils, benthic foraminifers, and geochemistry) of two sections
located in a restricted basin characterized by a limited water-depth
(the Causses Basin; Fig. 9) enabled us to reconstruct the fluctuations in
the nutrient concentration of the whole water column (i.e., in surface
waters and at the sea bottom), the photic zone structure, and the
deep-water oxygenation during the T-OAE. The geological record of
this event is characterized in the Causses Basin, as well as in various
other localities, by sediments depleted in CaCO3 but enriched in
organic matter, by a negative excursion of carbon isotopes, the virtual
absence of benthic fauna, and a drastic decrease in abundance of
calcareous nannofossils.
Nutrients were likely available all the time in the studied interval
within the Causses Basin. Indeed this basin was surrounded by
emerged lands that represented the source areas for nutrients. In spite
of the nutrient availability, nannoplankton production greatly varied
in the considered time interval. Calcareous nannofossil assemblages
are characterized by relatively high fertility index (Biscutaceae) in the
Late Pliensbachian and late Early Toarcian, namely prior to and after
the T-OAE. Similarly, small but significant peaks of opportunistic
foraminifers, adapted to high trophic conditions, are recorded in the
two periods. However, benthic fauna indicates that during the Late
Pliensbachian, the sea bottom was well oxygenated. Such conditions
likely prevented organic-matter preservation in the sediment. Cool
water temperatures in the Late Pliensbachian are probably responsible
for a higher concentration of dissolved oxygen in bottom waters, and
subsequent organic-matter remineralization. An important hiatus
spanning the topmost Pliensbachian and the basal Toarcian is
documented for the Causses Basin. This hiatus is associated with
low sea level and emersions in many basins surrounding the western
Tethys and might have had a glacio-eustatic origin, according to
Guex et al. (2001) and Morard et al. (2003). The following global
warming occurring in the Early Toarcian was coupled to an enhanced
hydrological cycle and riverine input, promoting the formation of low-
salinity water-bodies and, ultimately, a severe stratification for density
and widespread anoxia in all the epicontinental basins of the NW
Europe, including the Causses Basin. These conditions were favourable
to organic-matter accumulation and preservation in sediments. In the
Causses area, anoxia developed at the sea bottom first in the central
part of the basin, then the oxygen minimum zone expanded laterally
toward the shallower areas, and vertically towards the photic zone.
Anoxia development represented the most critical condition for
benthic organisms that temporarily disappeared during the T-OAE.
At the same time, surface water environments underwent very
stressing conditions testified by a severe drop in nannofossil abun-
dance, the temporary disappearance of taxa thriving in the lower
photic zone (like C. crassus), and peaks of taxa able to thrive in low-
salinity waters enriched in reduced nitrates (like Calyculus).
At the end of the Early Toarcian, stratification and anoxia were
removed from surface waters because of the development of storms, and
deep-dweller nannoplankton could thrive again. In the basin margins,
anoxic conditions at the sea bottom were probably alternating with
short-lived re-oxygenation, as indicated by the occurrence of abundant,
opportunist epifaunal foraminifers. However, in the deeper and confined
parts of the Causses Basin anoxia persisted as demonstrated by the
absence of benthic foraminifers in the more distal Saint-Paul-des-Fonts
section. The highest absolute abundance of nannofossils was recorded
after the T-OAE, along with high proportions of the coccolith taxa of
largest size. This datum seems to indicate that the contribution of
calcareous phytoplankton to the organic-matter fraction, that is mainly
marine in this interval, was significant. The results of this work indicate
that, although this interpretation has been recently challenged
(McArthur, 2007), the T-OAE was a global event that has been recorded
even in small and partly enclosed basins (like the Causses Basin).
Acknowledgements
We wish to warmly thank Alessandra Negri for inviting us to
submit a contribution to the special issue “Organic carbon rich
sediment through the Phanerozoic: Processes, Progresses and Per-
spectives”. The constructive remarks of Michaël Hermoso and an
anonymous reviewer greatly improved the quality of this manuscript.
F. Savignac is gratefully acknowledged for her assistance in Rock-Eval
analyses. Martine Fordant, Liana Goedde, Frédérique Bellec and
Gueorgui Ratzov are thanked for their precious help for foraminiferal
and geochemical analyses. We enjoyed the discussions with Serge
Elmi about stratigraphy all along this work. His advice and remarks
were invaluable to us. Publication No. UMR 5125-08.xxx.
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 Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 365–367
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j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o
Abstract of “The role of sea-level change and marine anoxia in the
Frasnian–Famennian (Late Devonian) mass extinction”☆
David P.G. Bond ⁎, Paul B. Wignall
School of Earth and Environment, University of Leeds, Leeds, LS2 9JT, United Kingdom
Introduction
The Frasnian–Famennian mass extinction (F–F, Late Devonian) is one
of the “big 5” faunal crises of the Phanerozoic with taxa being lost from a
broad range of marine habitats (Hallam and Wignall, 1997). Johnson et
al. (1985) proposed one of the first explicit links between marine anoxia,
transgression and mass extinction for the F–F mass extinction, a cause-
and-effect nexus which has been accepted by many. Extinction losses of
groups such as the ostracods, conodonts, and tentaculitoids are
contemporaneous with the widespread deposition of anoxic facies,
most notably the Upper Kellwasser Horizon of Germany, and many
workers have attributed the extinction to this phenomenon (e.g.
Joachimski and Buggisch, 1993; Becker and House, 1994; Levman and
von Bitter, 2002; Bond et al., 2004). Others (e.g. Copper, 1986; Sandberg
et al., 1988, 2002) prefer sea-level fall and cooling as an extinction
mechanism. The relationship between sea-level, the Upper Kellwasser
anoxic event and the contemporaneous mass extinction is a subject of
conflicting opinions (e.g. Hallam and Wignall, 1999 versus Sandberg et
al., 2002). Here, we examine the validity of the F–F boundary portion of
the classic Johnson et al. (1985) curve using facies analyses of sections
studied by the authors and recently-published data from the literature in
order to critically assess the role of sea-level change during the mass
extinction and its relationship with contemporary redox changes.
The Johnson et al. (1985) eustatic sea-level curve
The Johnson et al. (1985) eustatic sea-level curve identified two
major “depophases” (termed I and II) within the Devonian, each
consisting of 6 transgressive–regressive (T–R) cycles labelled a to f.
The Pragian to Frasnian was a time of rising sea-level, with the late
Frasnian being a period of second-order highstand, before sea-level
began to fall in the Famennian. T–R Cycle IId is of relevance here,
because this cycle straddles the F–F mass extinction interval (Fig. 1).
☆ The full version of this paper has been published in: Palaeogeography,
Palaeoclimatology, Palaeoecology 263, 2008, 107–118.
DOI of original article: 10.1016/j.palaeo.2008.02.015.
⁎ Corresponding author. Fax: +44 113 3435259.
E-mail address: d.bond@see.leeds.ac.uk (D.P.G. Bond).
0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.12.012
Johnson et al. (1985, p. 578) considered the sea-level rise component
of cycle IId to be:
“the greatest of Devonian transgressions… (because it) coincides with
the West Falls Group of New York and encompasses the Kellwasser
Limestone of Germany and the Matagne Shale of Belgium… (and)
comprises a pair of widely recognised transgressions”.
The two transgressions were separated by “a small-scale drop in
sea level” (Johnson et al., 1985, p. 584) and were followed by a major
regression in the Middle triangularis Zone. The first of the transgres-
sions occurred within the Lower gigas Zone and is contemporaneous
with the development of the Lower Kellwasser Horizon in Germany.
Unfortunately, Johnson et al. (1985) provided conflicting ages for the
second transgression and thus sowed the seeds of confusion in much
of the subsequent literature. In their figure 12 the second transgres-
sion was shown as beginning at the base of the Lower triangularis
Zone, but they state in their text that this transgression correlates with
the Upper Kellwasser Horizon. This began in the Uppermost gigas
Zone as correctly shown in their time-rock chart (Johnson et al., 1985,
figure 2). Johnson et al. (1985, p. 581) clearly stated that “the Frasnian–
early Famennian transgressive history supports an interpretation that
a succession of three rapid deepening events within and above IId, not
regression, caused many of the Frasnian extinctions”. We therefore
assume that their figure 12 was poorly drafted and that the second
transgression of T–R Cycle IId coincides with the development of the
Upper Kellwasser Horizon in the Uppermost gigas Zone, and thus with
the F–F mass extinction (Fig. 1).
Significant changes in the Late Devonian conodont zonation scheme
have occurred since 1985. The Lower to Upper gigas interval is now
approximated by the Early to Late rhenana Zones, whilst the Uppermost
gigas Zone has become the linguiformis Zone (Ziegler and Sandberg,
1990). The F–F boundary has also been redefined (Sandberg et al., 1988).
In 1985 it was placed at the Lower/Middle triangularis zonal boundary
but it is now placed at the base of the Lower (now more correctly called
Early) triangularis Zone. Thus, the second major transgression of the
Johnson et al. (1985) T–R cycle IId now begins within the linguiformis
Zone and the major regression at the top of the cycle is well within the
Famennian rather than at the old F–F boundary (Fig. 1).
Worldwide evidence for sea-level change
New facies analysis of sections in the USA (Nevada, Utah, New York
State) and Europe (France, Germany, Poland), and comparison with
366 D.P.G. Bond, P.B. Wignall / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 365–367
Fig. 1. The eustatic sea-level curve of Johnson et al. (1985), on the left as reproduced in their figure 12, and on the right as described in their text. Note Lower (L), Upper (U), and
Uppermost (Um) gigas Zones are now replaced by Early and Late rhenana and linguiformis Zones respectively. Lower (L), Middle (M) and Upper (U) triangularis Zones are now more
correctly termed Early, Middle, and Late triangularis Zones.
sections known from the literature in Canada, Australia and China
reveal several high-frequency relative sea-level changes in the late
Frasnian to earliest Famennian extinction interval. A clear signal of
major transgression is seen within the Early rhenana Zone in the Great
Basin of the western United States (e.g. drowning of the carbonate
platform, recorded as a transition from fossiliferous limestones to
laminated micrites in the Devils Gate section, and from fossiliferous
limestones to laminated shales in the Coyote Knolls section). This
transgression is also recorded in the eastern United States by the
development of the Pipe Creek Shale above the Nunda Sandstone, and
in western Europe at the onset of Lower Kellwasser anoxia. This is the
base of transgressive–regressive Cycle IId of the Johnson et al. (1985)
eustatic curve.
The transgression at the base of Cycle IId was curtailed by
regression and sequence boundary generation within the early lin-
guiformis Zone, recorded by hardground and karstification surfaces in
sections from Canada to Australia. This major eustatic fall probably
terminated platform carbonate deposition over wide areas, especially
in western North America.
The second of the pair of transgressions in Cycle IId begins in the
later linguiformis Zone, and is recorded by the development of
organic-rich shale or bituminous limestone facies in sections as
widespread as the western and eastern United States (e.g. Whiterock
Canyon and Beaver Meadow Creek respectively), Canada (the Moose
River Basin of Ontario (Levman and von Bitter, 2002)), France (e.g.
Coumiac and La Serre), Poland (Kowala Quarry), and Germany
(Steinbruch Benner). In South China, this transgression is recorded
by the infilling of a prominent palaeokarst surface with dark grey
limestones of late linguiformis Zone age (Chen and Tucker, 2003,
2004). In Australia, two late Frasnian transgressions are manifest in
the Canning Basin as the development of upper marginal-slope facies
in reef-margin settings at a time of backstepping stratal geometry,
and, using carbon isotope stratigraphy, these have recently been dated
as contemporaneous with the Kellwasser transgressions in Europe
(Stephens and Sumner, 2003).
This linguiformis Zone transgression is significant because it is
associated with the expansion of anoxic deposition, known as the Upper
Kellwasser Event. Johnson et al.'s (1985) original transgression–anoxia–
extinction link is thus supported, although some extinction losses of
platform carbonate biota during the preceeding regression cannot be
ruled out. Claims for a latest Frasnian regression (e.g. Sandberg et al.,
2002) are not supported, and probably reflect poor biostratigraphic
dating of the early linguiformis Zone sequence boundary.
Since the publication of the original version of this manuscript, the
latest Exxon Palaeozoic sea-level curve has been published (Haq and
Schutter, 2008). Although by necessity this curve is produced at a
somewhat lower resolution than our study, it clearly indicates two
transgressions in the late Frasnian, separated by a small-scale drop in
sea-level, and terminated by major regression in the earliest
Famennian. Thus, the Haq and Schutter (2008) sea-level curve
correlates well with the history described above.
Anoxia and mass extinction
The close association of transgression, the development of anoxic
facies, and the Late Devonian mass extinction has lead many authors
to attribute a cause-and-effect relationship (e.g. Buggisch, 1972;
House, 1985; Casier, 1987; Geldsetzer et al., 1987; Goodfellow et al.,
1989; Walliser et al., 1989; Buggisch, 1991; Becker, 1993; Joachimski
and Buggisch, 1993; Becker and House, 1994; Joachimski et al., 2001,
2002; Levman and von Bitter, 2002; Chen and Tucker, 2003; Bond
et al., 2004; Tribovillard et al., 2004; Bond and Wignall, 2005; Riquier
et al., 2005; Bond, 2006; Pujol et al., 2006). Sea level does not change
in isolation within the earth-surface system and it is likely that the
major eustatic changes associated with F–F mass extinction indicate
destabilisation of the climate and C cycle (e.g. Copper, 1986; Buggisch,
1991; Joachimski and Buggisch, 1993; Becker and House, 1994; Algeo
et al., 1995; Algeo and Scheckler, 1998; Streel et al., 2000; Joachimski
et al., 2002; Goddéris and Joachimski, 2004; Averbuch et al., 2005;
Chen et al., 2005; Riquier et al., 2005).
The transgression–anoxia–extinction scenario invoked here and by
those authors cited above appears to be a pattern which was repeated
several times during the Devonian. Brett and Baird (1995) recognised
six Ecological–Evolutionary subunits in the Early Devonian to Frasnian
interval, at least five of which were apparently terminated by
widespread anoxic highstands. Thus, there were probably several
lesser extinctions during the Devonian, and the Frasnian–Famennian
event was merely a more intense manifestation of this scenario.
Acknowledgements
The authors wish to thank Steve Kershaw and an anonymous
reviewer for their helpful comments on the original version of this
manuscript. We also would like to thank those who assisted our
fieldwork, which was part of the first author's NERC-funded PhD project:
Dieter Korn, Jared Morrow, Jeff Over, Greg Racki, and Michal Zaton.
 D.P.G. Bond, P.B. Wignall / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 365–367 367

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Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Black shale deposition in an Upper Ordovician–Silurian permanently stratified,

peri-glacial basin, southern Jordan
Howard A. Armstrong a,⁎, Geoffrey D. Abbott b, Brian R. Turner a, Issa M. Makhlouf c,
Aminu Bayawa Muhammad b, Nikolai Pedentchouk d, Henning Peters e
a
Palaeozoic Environments Group, Department of Earth Sciences, Durham University, Science Laboratories, South Road, Durham DH1 3LE, UK
b
School of Civil Engineering and Geosciences, Drummond Building, University of Newcastle upon Tyne, Newcastle upon Tyne NE1 7RU, UK
c
Department of Earth and Environmental Sciences, Hashemite University, Zarqa, Jordan
d
Petroleum Reservoir Group (PRG), Department of Geology and Geophysics, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
e
Research Center for Ocean Margins (RCOM), University of Bremen, Post Box 330 440, 28334 Bremen, Germany

A R T I C L E I N F O A B S T R A C T

Article history: The Lower Palaeozoic (Upper Ordovician–Silurian) succession of North Africa contains one of the world's
Received 1 October 2007 most prolific black shale source rocks, yet the origin of these rocks remains contentious. The black shale of
Received in revised form 8 May 2008 the Batra Formation in Jordan was deposited at high palaeolatitude during rapid Hirnantian to early Silurian
Accepted 15 May 2008
deglaciation. Here we report geological and organic geochemical results that provide evidence for an increase
in photic zone primary productivity during ice melting. The decay of this organic matter through oxidative
Keywords:
Black shales
respiration resulted in euxinia, which enhanced the potential for organic matter preservation. The occurrence
Silurian of isorenieratane in all samples indicates euxinia extended from the photic zone to the sediment water
Peri-glacial interface. The stratified basins and fjords of east Antarctica provide a likely modern analogue.
Jordan © 2008 Elsevier B.V. All rights reserved.

1. Introduction evidence for productivity changes, anoxia/euxinia and the increased

The deposition of marine black shale and the enhanced storage of
organic carbon (OC) in the geological record indicate fundamental
changes in the functioning of biogeochemical cycles and their
feedbacks during extreme climate modes and transitions (Beckmann
et al., 2005a; Page et al., 2007). Our understanding of the response of
the marine environment during these climate states can only be
gained from a study of deep time analogues.
The Upper Ordovician–Lower Silurian succession of North Africa
and Arabia contains thick (∼ 20 m), organic carbon (OC)-rich (up to
15% total organic carbon (TOC)) black shale, widely known as the “hot
shales,” which are the source of ∼30% of the world's oil (Lüning et al.,
2000, 2006). The origin of these deposits remains contentious
(Armstrong et al., 2005, 2006). The lower hot shale overlies glacial
and glacio-marine sediments deposited during the Hirnantian glacia-
tion (∼445 Ma) and have been linked to either, nutrient enrichment of
shallow marine environments during coastal upwelling (Lüning et al.,
2000) or, freshening by deglacial meltwater (Armstrong et al., 2005).
Here we report data from Jordan that confirms the lower hot shale
was deposited in a stratified, ice margin basin during Hirnantian to
early Silurian deglaciation (Armstrong et al., 2005). We relate deglacial
sea level rise (at Milankovitch timescales) and melt water flux to
⁎ Corresponding author.
E-mail address: h.a.armstrong@durham.ac.uk (H.A. Armstrong).
burial of organic matter. Bulk δ13C and total organic carbon (%TOC) are
taken to reflect productivity changes. The presence of isorenieratane
(XXIII; see Appendix A for structure), a biomarker of green sulphur
bacteria, is indicative of photic zone euxinia. Likely modern analogues
are the seasonally isolated basins of east Antarctica. A similar
interdisciplinary approach is necessary to elucidate the nature of
these deposits elsewhere on the Gondwana margin.
2. Stratigraphical and geological context
The Lower Palaeozoic succession in southern Jordan includes some
750–800 m of well exposed Ordovician siliciclastic sediments deposited
on the margins of the North African (Gondwana) in terrestrial to subtidal
marginal marine and shelf environments (Amireh et al., 2001; Makhlouf,
1995; Powell et al., 1994; Fig. 1). During the Late Ordovician Jordan was
located in a high latitude, east Gondwana setting, 60° S of the equator
(Cocks and Torsvik, 2002), less than 100 km from the margins of a ter-
restrial ice sheet in northwest Saudi Arabia. This ice sheet was char-
acterised by two major phases of ice advance and retreat (Vaslet, 1990)
both marked by erosional unconformities (Vaslet, 1990; Figs. 1 and 2). The
first major glacial ice incised into permafrost-hardened and glacially
loaded, Tubeiliyat shoreface and nearshore shelf deposits, preferentially
excavating NW–SE trending major fault-controlled depressions, cutting a
steep-sided U-shaped valley (Turner et al., 2005). This ice advance
correlates with the first glacial advance in northwest Saudi Arabia (Vaslet,
1990; Miller and Mansour, 2007; Fig. 3), and was followed by deglaciation,

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.05.005
 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377 369

Fig. 1. Lithostratigraphy and chronostratigraphy for the Ordovician and Silurian of Jordan and Saudi Arabia, showing generalised depositional environments for outcrops in the
Southern Desert region of Jordan (redrawn from Turner et al., 2005). Subdivision of the Ammar Formation into the Lower and Upper Ammar is based on Abed et al. (1993).

Fig. 2. Generalised section of the glacial and deglacial succession in the Southern Desert region of Jordan and northwest Saudi Arabia showing the stratigraphy and sediment fill of the
glacially incised palaeovalley systems. Section A is located 0.5 km southwest of Jebel Umier (29° 34′ N, 35° 53′ E) and Section B is from Jebel Ammar (29° 34′ N, 35° 52′ E). Section C is
from northwest Saudi Arabia and is based on Vaslet (1990); reproduced with permission from Turner et al. (2005).
370 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377
Fig. 3. Palaeogeographical reconstruction of eastern Gondwana, during the late Ordovician,
showing the ice sheet (shaded) and the location of Jordan and Saudi Arabia (redrawn from
Sutcliffe et al., 2000).
a rise in relative sea level and transgressive filling of the palaeovalley. The
latter is recorded by a thin, reworked bottom lag of glaciofluvial
sandstones, overlain by thick, transgressive, shoreface sandstones. Late
transgressive filling of the palaeovalley was interrupted by a second and
possibly a third subsidiary glacial advance producing a glacially polished
and grooved surface with intersecting glacial striations, indicating ice flow
from the west and northwest (Turner et al., 2005).
The fourth glacial advance produced a regionally extensive low-
stand tunnel valley beneath the ice sheet (Turner et al., 2002). This was
subsequently preserved as a palaeovalley incised into the lower
palaeovalley-fill deposits or, where this is missing, into the top of the
Tubeiliyat Formation. This ice advance correlates with the second
major ice advance in Saudi Arabia (Vaslet, 1990), where the Sarah
Formation similarly records a complex record of ice advance and
retreat (Miller and Mansour, 2007). The pattern of “major” ice advances
interspersed by smaller-scale events has been interpreted as reflecting
eccentricity and obliquity moderated ice volume changes (Sutcliffe
et al., 2000; Armstrong, 2007). Following melting of the fourth ice
sheet the upper palaeovalley filled with transgressive glaciofluvial
sandstones, marine shoreface sandstones (Turner et al., 2005) and
finally black shale of the Batra Formation (Armstrong et al., 2005).
The Batra Formation is ∼40–120 m thick, and in the Southern
Desert region of Jordan it conformably overlies the Ammar Formation
or disconformably overlies the Tubeiliyat Formation (Fig. 1). The lower
part of the formation is found in many shallow exploration wells, and
was restricted to fault-bounded graben structures (Powell et al., 1994;
Turner et al., 2005). The formation is variably graptolitic and contains
sparse thin-shelled bivalves and rare trilobites (Masri, 1988).
In the type area the lower part of the Batra Formation comprises
17.44 m of monotonous, OC-rich black shale, which in thin section
comprise laminated, black siltstone to dark grey homogeneous
claystone couplets. The parallel laminated siltstones are OC-rich, and
grade upwards into mudstone, with irregular patches of siltstone
(? starved ripples) and homogeneous claystones. The couplets were
interpreted as distal turbidites by Armstrong et al. (2005). The absence of
bioturbation indicates anoxic/euxinic bottom water during deposition
(e.g. Droser and Bottjer, 1986). The laminites, characteristic of the whole
formation, contain pyrite framboids and marcasite concretions through-
out, confirming a euxinic depositional environment (Wignall, 1994).
Andrews (1991) reviewed the biostratigraphy of this formation from
surface exposures and exploration wells and concluded that the entire
formation ranged in age from Ashgill (persculptus Biozone) to the mid-
Wenlock. Graptolites from the lower part of the core have been identified
(see also Loydell, 2007). Samples from a depth of 46.62 m (close to
the base of the Batra Formation in well BG-14) contain the graptolite
Neodiplograptus apographon typical of the middle and upper subzones of
the ascensus-acuminatus biozone (sensu Storch, 1990) and indicate an
earliest Silurian age. Graptolites collected at 42.82 m (4.02 m above base
of formation) and 41.57 m (5.27 m above the base of the formation)
contain Normalograptus parvulus. N. parvulus ranges through the pers-
culptus to acuminatus biozones of Hirnantian to Rhuddanian (Llandovery)
age (Zalasiewicz and Tunnicliff,1994, Fig. 3). These age assignments allow
the correlation of the transgressive fill of the upper palaeovalley in Jordan
with the Hirnantian to early Llandovery (Rhuddanian) global eustatic sea
level rise (Cocks and Rickards, 1988; Loydell, 1998).
Armstrong et al. (2005) concluded the base of the black shale is
coincident with the maximum flooding of the first post-glacial highstand
(cf Lüning et al., 2000). The fill of the upper palaeovalley was considered
as an “expanding puddle” as originally defined by Wignall (1991).
3. Materials and methods
Here we use carbon isotopic, biomarker and Rock-Eval analyses on
black shale from the lower Batra Formation (Jordan) to establish water
column redox conditions. Core samples were obtained from the
immature (average Tmax value of 419 °C), OC-rich lower 18 m section of
the Batra Formation in the type area of Wadi Batn el Ghul (well BG14;
Table 1) from the Southern Desert region of Jordan (29°30′50.4″ N
35°57′41″ E; Armstrong et al., 2005).
3.1. Total organic carbon (TOC) and Rock-Eval pyrolysis
The TOC contents of the dried samples were measured using a
calibrated LECO CS-244 elemental analyser. Each sample was analysed in
duplicate and standard material was analysed after every 10 analytical
samples to ensure that the analyser maintained its calibration. Rock-Eval
pyrolysis was carried out using a Delsi Oil Show Analyser. Each sample
was pyrolysed in duplicate so that the mean values of the amounts of
hydrocarbons detected under the S1 and S2 peaks as well as the
temperature Tmax, corresponding to the temperature at which the
maximum of the S2 hydrocarbon generation occurs during pyrolysis,
could be measured. Standard (5.51% TOC; 0.27 mg HC/g of rock S1;
13.59 mg HC/g of rock S2; and 430 °C Tmax) and then blank samples were
pyrolysed under these same conditions to ensure that the measure-
ments of the unknown quantities were as precise as possible. The
average standard deviations with respect to S1, S2 and Tmax were
0.05 mg HC/g of rock, 0.43 mg HC/g of rock and 2.3 °C respectively.
3.2. Bulk stable carbon isotope analysis
13 12
C/ C ratios (δ13C) were measured on bulk sediments after removal
of the inorganic carbonates with dilute HCl using automated online
combustion followed by conventional isotope ratio-mass spectrometry
in a VG TripleTrap and Optima dual-inlet mass spectrometer, with δ13C
values calculated to the Vienna Peedee belemnite (VPDB) scale using a
within-run laboratory standard (cellulose, Sigma Chemical prod. no. C-
6413) calibrated against NBS-19 and NBS-22. Replicate analysis of well-
mixed samples indicated a precision of ±0.1‰ (1 S.D.).
3.3. Gas chromatography (GC)/gas chromatography–mass spectrometry
(GC-MS)
The powdered black shales were Soxhlet extracted with dichlor-
omethane/methanol (93:7; v/v) for 48 h. An aliquot of each total extract
was separated by thin layer chromatography (TLC, Kieselgel 60G, 0.5 mm
thickness) using light petroleum ether (boiling point is from 40 to 60 °C)
into aliphatic hydrocarbon, aromatic hydrocarbon and polar fractions.
The aliphatic and aromatic hydrocarbon fractions were analysed using a
Hewlett-Packard HP5890 gas chromatograph (GC) equipped with a
flame ionisation detector and a fused silica capillary column
 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377 371

Table 1 Steranes and hopanes were identified using published mass spectra
Late Ordovician black shales from a Batra Formation (southern Jordan) borehole (BG14) and relative retention times (e.g. Peters et al., 2005). Isorenieratane
giving sample # and position in the stratigraphical column
(XXIII) was identified by its mass spectrum and by GC-MS co-injection
Sample Height above base of Batra Formation (m) Depth in core (m) experiments on an HP-1 stationary phase (authentic standard of
8402-77 16.76 30.08 isorenieratane (XXIII) was supplied courtesy of S. Schouten, Nether-
3402-19 15.28 31.56 lands Institute for Sea Research, Den Burg, Netherlands). The GC-MS
3402-18 15.14 31.70
results from the co-injection experiments are presented in Fig. 5.
3402-17 14.84 32.00
3402-16 14.34 32.50
3402-15 12.94 33.90 4. Results
3402-14 11.74 35.10
3402-13 10.94 35.90 The presence of parallel laminations accompanied by an absence
8402-75 9.84 37.00
8402-73 9.52 37.32
of bioturbation throughout the section indicates euxinic bottom
8402-74 9.27 37.57 waters during deposition. All samples typically contain acritarchs
8402-72 8.77 38.07 and graptolites (Keegan et al., 1990) indicating a primarily marine
8402-68 7.77 39.07 phytoplanktonic and zooplanktonic source of Type II kerogen. The
8402-67 7.52 39.32
percentage of total organic carbon (% TOC) increases as a function of
8402-66 7.27 39.57
8402-64 6.77 40.07 height above the base of the Batra Formation (Fig. 6A). This section
8402-63 6.52 40.32 is OC-rich with a stepwise increase in %TOC from ∼ 1% to ∼ 3% and
8402-62 6.27 40.57 from ∼ 3% to ∼ 9% at 6.27 m and 12.94 m respectively above the base
8402-61 6.02 40.82 of the section (Armstrong et al., 2005). Figs. 6B and 7 show that the
8402-60 5.77 41.07
Rock-Eval hydrogen index (HI) values of the samples have a range of
8402-59 5.52 41.32
8402-53 4.02 42.82 156 to 402 mg HC/g TOC (mean value = 283 mg HC/g TOC). The δ13C
8402-52 3.77 43.07 of bulk organic matter show a range of − 30.8 to − 29.6‰ with
fluctuations of up to 0.4‰ and a positive shift of 1.4‰ up the section
with the largest increase (∼ 1‰) apparent in the two uppermost
(30 m × 0.25 mm i.d.) coated with either HP-1 or HP-5 stationary phase samples (Fig. 6D).
(film thickness of 0.25 µm). The carrier gas was hydrogen, and the oven The regular sterane carbon number distributions are such that C29 N C27
temperature was held at 50 °C for 2 min and then heated at a rate of 4 °C/ C27 NN C28, where the average value of the C28/C29 steranes ratio is 0.27,
min to 300 °C, at which it was held for 20 min (Fig. 4). which agrees with previous observations that generally this particular
GC-MS was performed using a Hewlett-Packard HP5890II GC ratio is less than about 0.35 for samples older than Silurian (Grantham and
coupled with a Hewlett-Packard 5972 mass spectrometer (ionising Wakefield, 1988). Both the sterane and 17α-hopane distributions indicate
voltage of 70 eV and with the source temperature at 160 °C). The GC thermally immature organic matter and do not vary significantly
was fitted with a fused silica capillary column (30 m × 0.25 mm i.d.) throughout the section. Maxima in the regular steranes/17α-hopanes
coated with either HP-1 or HP-5 stationary phase (film thickness of (Frimmel et al., 2004) occur at ∼6.5 m and 12.94 m above the base of the
0.25 µm). The carrier gas was helium, and for analysis of the aliphatic formation and coincide with the stepped increases in %TOC suggesting
hydrocarbons (see Fig. 4) the oven temperature was held at 40 °C for major contributions to the organic matter from plankton (Fig. 6C).
2 min and then heated at a rate of 4 °C/min to 300 °C at which it was The mass chromatogram for m/z 133 from the aromatic hydrocarbon
held for 20 min. The following oven temperature programme was fraction (Fig. 7) reveals a pseudo-homologous series of aryl isoprenoids
used for the analysis of the aromatic hydrocarbons (primarily for the up to C26 (see I through to X in Fig. 7 and Table 2) as well as the presence
assignment of isorenieratane XXIII): the oven was held at 60 °C for of aryl isoprenoids with additional aromatic rings (see XI and XVI in
2 min and then heated to 240 °C at 10 °C/min, further heated to 315 °C Fig. 7 and Table 2). The relative amounts of the different components
at 4 °C/min where it was held at the final temperature for 50 min. remains the same throughout the profile where the C17, C20, C21, C22

Fig. 4. Total ion chromatogram (TIC) of aliphatic hydrocarbon fraction from Upper Ordovician black shale from 16.76 m (sample 8402-77) above the base of the formation in BG-14
borehole. Pr = pristane, Ph = phytane; numbers denote total number of carbon atoms in the n-alkanes.
372 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377

Fig. 5. GC-MS ion chromatogram of m/z 133 of aromatic hydrocarbon fraction from Upper Ordovician black shale (sample 3402-15) taken at 33.9 m in the core, 12.94 m above the base
of the formation. (A) after and (B) before co-injection with an authentic standard of isorenieratane (XXIII; courtesy of S. Schouten, Netherlands Institute for Sea Research (NIOZ), Den
Burg, Netherlands) showing enhancement of peak after co-injection. (C) is mass spectrum of isorenieratane (XXIII) from the sample.

members have reduced abundances. This distribution is similar to
that observed in Upper Devonian sediments (Hartgers et al., 1994) but
differs from that in much older mid-Proterozoic bitumens (Brocks
et al., 2005). There are also less abundant C32, C33 and C40 diaryl
isoprenoids both with and without an additional aromatic ring (see
XVII through to XXIII in Fig. 7 and Table 2). Isorenieratane (XXIII) was
present throughout the core and its identity was also confirmed by
co-elution with an authentic standard on a range of stationary phases
(Sinninghe Damsté et al., 2001).
5. Discussion
The deposition of sedimentary organic carbon in the lower Batra
Formation is delimited by stepped increases (approximate doubling at
 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377 373

Fig. 6. Composite plot of bulk organic carbon, biomarker and bulk stable carbon isotopic data. (A) Total organic carbon (TOC) content of the bulk sediment. (B) Hydrogen index (HI) of
the bulk sediment (mg hydrocarbons (HC)/g TOC). (C) Steranes/17α-hopanes ratio shows its highest value at 12.94 m above the base of the Batra formation. (D) δ13C values of organic
carbon (OC) versus Vienna Peedee belemnite (VPDB) in parts per mil (‰).

each step) in %TOC up succession. %TOC has been found to correlate
well with more direct measures of photosynthetic primary produc-
tivity such as total chlorophyll-a or total steryl chlorine esters (Nara
et al., 2005) and organic mass accumulation rate (Tyson, 1995;
Vilinski and Domack, 1998; Twichell et al., 2002; Meyers and
Arnaboldi, 2005). A longer-term trend towards more fractionated
values up succession reflects a progressive increase in the sedimen-
tation of 12C-enriched organic matter.
Hydrogen index (HI) is a measure of hydrogen-richness and depends
on the nature of the original organic matter and the degree of
preservation during diagenesis (Peters, 1986; Bordenave et al., 1993).
Millimetre-scale laminations and presence of macroscopic pyrite
through the section suggests euxinia and that organic matter preserva-
tion potential was high throughout deposition. Our bulk rock HI values
are similar to those reported from Mediterranean, Pliocene–Pleistocene
(b3 myr old) immature sapropels which have HI values of ∼400 mg HC/g
TOC (Tyson, 1995). Bulk HI and organic matter δ13C values do not covary
(Fig. 6B and D); and this with the unchanging nature of kerogen type
through the section, suggests variations in HI reflect the changing extent
of organic matter preservation (see Tyson, 1995).
Peaks in steranes/17α-hopanes ratio (N1) coincide with the stepped
changes in %TOC, that provide a coherent signal of primary productivity.
We therefore conclude the changes in %TOC reflect changes in plankton
primary productivity in the photic zone. The decay of this organic matter
through oxidative respiration resulted in anoxia and euxinia, which
enhanced the potential for organic matter preservation.
Our bulk δ13C values fall within the range for modern phytoplanktonic
algae (Schidlowski, 1988) and for bulk organic matter in the Southern
Ocean at 0 °C (Rau et al., 1989; Bentaleb and Fontugne, 1998; Bentaleb
et al., 1998; Lourey et al., 2004). Increasingly more fractionated bulk
organic matter δ13C values occur up section with no change in kerogen
type. In ice margin basins at the present day changes in δ13C are usually
associated with a decreased CO2 availability in response to (a) decreased
supply by diffusive limitation, or (b) increased demand because of higher

Fig. 7. Typical GC-MS summed mass chromatogram of m/z 133 + 134 from the aromatic hydrocarbon fraction isolated from the shale organic extract at 11.64 m above the base of the
Batra Formation. This trace shows the C40 biomarker isorenieratane (XXIII). Roman numerals refer to compounds indicated in Appendix A and Table 2.
374 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377

Table levels
light 2 and growth rates (Laws et al.,1995; McMinn et al.,1999) and/or stratification is maintained in these basins by an increase in salinity
Details of mass spectral
the increased identifications
availability of I–XXIII
of (trace) nutrients at the time of plankton (Gibson, 1999) resulting from brine exclusion during sea ice formation.
13
growth
Peak label(Redfield et al.,
Molecular 1963). Molecular
formula Severe fractionation
ion(m/z) of δfragment
Major C is known to
ions (m/z) During the winter, a thermocline convection cell develops directly
I C13H20 176 133/134 beneath the ice cover and penetrates progressively deeper into the
II C14H22 190 133/134 basin throughout winter. At the end of the period of ice formation the
III C15H24 204 133/134 convection cell breaks down and stratification of the surface water
IV C16H26 218 133/134
occurs. When the ice melts completely, lenses of relatively fresh
V C17H28 232 133/134
VI C18H30 246 133/134 water cap the basins; this reduces the effect of wind mixing, with a
VII C19H32 260 133/134 net result of stabilising the basin stratification, with anoxia develop-
VIII C20H34 274 133/134 ing at depth. The effect of, increasing water level in the basins or
IX ? 226 133/134, 147, 220 decreasing maximum ice thickness during the summer results in a
X C21H36 288 133/134, 220
XI C21H27 280 133/134
shallowing of the mixocline and chemocline (Gibson, 1999). The
XII ? 302 133/134, 185, 253 nature of the stratification in these basins (Gibson, 1999; McMinn
XIII C22H29 294 133/134 et al., 2001) is therefore similar to those reported from the many
XIV ? 336 133/134, 239, 253 permanently stratified basins around the world including the Red Sea
XV ? 350 133/134, 195, 239, 253
(Hartmann et al., 1998), the Cariaco Trench, the Black Sea, and fjords
XVI C26H32 344 133/134, 169/170, 253
XVII C32H42 426 133/134, 119, 173 of Scandinavia (Skei, 1983; Lindholm, 1996).
XVIII C32H50 434 133/134 We envisage the geological history of the Batra Basin and its included
XIX C33H42 448 133/134 sediments to be directly controlled by ice margin processes. On ice
XIX C33H42 448 133/134 melting and retreat the exposed upper palaeovalley became a conduit for
XX C40H58 538 133/134, 237
ice meltwater. The basin was initially isolated from shallow marine
XXI C40H58 538 133/134, 173
XXII C40H66 546 133/134, 235 waters, likely silled and glaciofluvial sediments were deposited. As the
XXIII C40H66 546 133/134 effects of isostatic rebound waned and sea level rose, the basin was
flushed by marine waters. On short timescales we envisage the basin
became stratified due to the formation and melting of sea ice (Fig. 8). The
millimetre-scale laminations in the black shales may reflect seasonal to
occur naturally in either intense phytoplankton blooms (Dunbar and decadal (? millennial) changes in sea ice cover. On the longer term,
Leventer, 1992) or within sea ice (Dunbar and Leventer, 1992; McMinn periods of increased surface primary productivity occurred when
et al.,1999). Natural values for modern Southern Ocean phytoplankton can prolonged ice free conditions prevailed and/or, fluxes of freshwater and
be as low as −25‰ (Rau et al., 1991). While highly fractionated values as nutrients entered the already stratified, euxinic marine basin. Stratigra-
high as −12‰ have been recorded from sea ice (Dunbar and Leventer, phical evidence (Armstrong et al., 2005) is consistent with modelling
1992; McMinn et al., 1999). Thus when sea ice melts it not only delivers a results (Herrmann et al., 2003) and indicates the frequency of melting
pulse of sediment and nutrients, but also organic matter that has a more events during the late Hirnantian deglaciation was likely to have occurred
fractionated δ13C signature (Gibson, 1999). on an obliquity (∼40 kyr) timescale. The black shales of the Batra Basin
A pattern of long-term covariance of more fractionated δ13C and record a few hundred thousand years of water column stratification and
increasing %TOC has also been reported in Cretaceous (Late Cenoma- basin euxinia during deglacial highstand. This represents one of the
nian/Turonian) black shale in the North Atlantic, deposited during oldest peri-glacial permanently stratified basins yet described.
periods of enhanced continental run-off (Beckmann et al., 2005a,b).
Here the pattern has been interpreted to indicate organic carbon 6. Conclusions
sequestration to the sediment was cumulative through the deposi-
tional event (Kuypers et al., 2002). Sedimentology, geological setting and organic geochemical
We therefore consider the more fractionated δ13C values through proxy data indicate the Batra Formation black shale in Jordan was
the lower Batra section to represent CO2 limitation and increased deposited in a permanently stratified, ice margin, marine basin that
productivity as nutrients and isotopically light carbon were supplied existed for a few hundred thousand years. Euxinia extended into the
by melt water. The long-term trend towards more fractionated values photic zone enhancing sedimentary carbon preservation and
reflects a progressive increase in the sedimentation of 12C-enriched sedimentation. Ice melting and/or, fluxes of freshwater and
organic matter during progressive deglaciation. nutrients resulted in enhanced photic zone primary productivity
The presence of isorenieratene derivatives in black shales has been
widely considered diagnostic of green sulphur reducing bacteria
(Chlorobiaceae and Chromatiaceae) and is used as evidence for photic
zone euxinia (e.g. Sinninghe Damsté and Köster, 1998). Further, pyrite
is common through the section. In the modern ocean (Killops and
Killops, 1993) the depth of the sulphate reduction zone depends on
the amount of organic matter influx from the euphotic zone and may
be relatively shallow (b20 m) in highly productive areas, where
sulphate is rapidly depleted (Brocks et al., 2005). The depth to the
chemocline in the Batra Basin may have been shallower than the
∼ 50 m found in the Black Sea at the present day (Murray et al., 1989).
The greatest concentration of stratified water bodies in high
latitudes, and possibly the world, is found in the Vestfold Hills of
Antarctica. Here meromictic lakes, isolated marine basins and fjords
occur (Burton,1981; Burke and Burton,1988a; Gallagher et al., 1989) and
seasonal anoxia is developed in these settings. These basins formed
following the retreat of the continental ice sheet ∼ 10 000 years ago, Fig. 8. Conceptual model of the open water (ice free), stratified water column during the
when isostatic rebound occurred at a faster rate than sea level rise, and deposition of the lower “hot shales” in the Batra Basin. This is based in part on that found
the land emerged from the sea (Burke and Burton, 1988b). Seasonal in modern ice margin basins in the Vestfold Hills, east Antarctica (Gibson, 1999, Fig. 7).
 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377
and organic matter sedimentation. The seasonally isolated basins and
anoxic fjords of east Antarctica provide a likely modern analogue,
though these are b10 000 years old. Black shale was patchily
deposited along the entire northern Gondwana margin during the
Silurian. Similarly detailed interdisciplinary studies are required to
test whether coastal upwelling can be invoked to explain the origin of
any of these deposits.
Acknowledgements
The National Resources Authority of Jordan provided access to the
core. We acknowledge support from our host institutions and the
Natural Environment Research Council for research funds including
Appendix A. Structures of isorenieratene derivatives
375
JREI awards. Dr David Loydell (University of Portsmouth) and Dr Mark
Williams (University of Leicester) kindly identified the graptolites. TOC
measurements were conducted by Dr D.M. Jones (University of
Newcastle upon Tyne) and isotopic analyses by Prof. M. Leng (NERC
Isotope Geosciences Laboratory). We thank Christine Jeans for the
preparation of the Figures and B. Bowler for technical input. H.P.
acknowledges the European Commission Research Directorates Gen-
eral for a Marie Curie Host Fellowship held at the University of
Newcastle upon Tyne. A.B.M. was supported by the Petroleum
Technology Development Fund, Nigeria. H.A.A. and B.R.T. acknowledge
funding from the Natural Environment Research Council. This is a
contribution to IGCP Project 503. We thank Lorenz Schwark and an
anonymous referee for their helpful suggestions.
376 H.A. Armstrong et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 368–377
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Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / p a l a e o

Palynology, organic geochemistry and carbon isotope analysis of a latest Ordovician

through Silurian clastic succession from borehole Tt1, Ghadamis Basin, southern
Tunisia, North Africa: Palaeoenvironmental interpretation
Marco Vecoli a,⁎, Armelle Riboulleau b, Gerard J.M. Versteegh c
a
Research team UMR 8157, CNRS, University of Lille 1, Villeneuve d'Ascq, F-59655, France
b
Research team UMR 8157, PBDS, University of Lille 1, Bâtiment SN5, 59655 Villeneuve d'Ascq, F-59655, France
c
Organic Geochemistry Unit, Faculty of Geosciences, Bremen University, P.O. Box 330440 D-28334 Bremen, Germany

A R T I C L E I N F O A B S T R A C T

Article history: Palynological and palynofacies analyses combined with organic carbon isotope measurements have been
Received 12 December 2007 performed on terminal Ordovician through Silurian clastic sediments from the North African margin of
Received in revised form 26 May 2008 Gondwana (southern Tunisia). A first carbon isotopic signal (δ13Corg) from Gondwanan Silurian sedimentary
Accepted 27 May 2008
sequences is presented, showing interesting correlation with existing coeval isotopic curves from other areas.
Changes in lithology, palynofacies characteristics, palynomorph diversity, carbon isotope developments, and
Keywords:
Palynomorphs
organic geochemistry parameters appear to be all causally linked, and to reflect changes in palaeoceano-
Palynofacies graphic conditions. In particular, the detailed chronostratigraphic correlation and the observed similarities in
Carbon isotopes patterns of carbon isotopic developments and (palyno- and litho-) facies changes through the study section
Bioevents has permitted to identify the supposedly global earliest Wenlock (“Ireviken Event”) and late Ludlow (“Lau
Black shales Event”) isotopic excursions for the first time in high-latitude Gondwana. This confirms that these excursions
Productivity were linked to global changes in the oceanic system.
Gondwana The present results suggest that from Rhuddanian to early Wenlock times, an extended period of black shale
Ordovician
deposition occurred over the North African Gondwanan margin, progressively transgressing from basin
Silurian
palaeodepressions to basin palaeohighs. Palynofacies and organic geochemistry support a coastal upwelling-
promoted productivity increase during this interval, associated to a decrease in diversity of the marine
microplanktonic communities. The earliest Wenlock strong positive isotopic shift appears associated with
this protracted period of massive black shale deposition, and thus of organic carbon burial, on continental
platforms located in high-latitude settings. This could well explain the apparent paradox between excessive
carbonate deposition simultaneous to a carbon isotopic shift towards lighter values observed in low
palaeolatitude localities (Laurentia and Baltica). the strong, distinct isotope excursion occurring in late
Ludlow times is possibly linked to the well know Lau Event. Evidence for extensive organic carbon burial is
lacking to explain this strong excursion. Some significant changes in the marine palynomorph communities
are recorded in connection to the increase in stable isotope values (δ13Corg). Additionally, a strong correlation
between abundance of terrestrially derived palynomorphs (miospores) and δ13Corg development is recorded
which seems to support increased clastic input from a terrestrial source.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Ordovician-Silurian sedimentary sequences at the northern mar-
gin of western Gondwana record palaeoclimatic and palaeoenviron-
mental changes of global significance. These include the end of the
severe and short-lived Late Ordovician glaciation which caused one of
the major faunal extinctions of the Phanerozoic, the successive return
to pre-glacial, globally warmer conditions, widespread deposition of
⁎ Corresponding author.
E-mail address: Marco.Vecoli@univ-lille1.fr (M. Vecoli).
black shales with exceptionally high organic content (“hot shales”:
Lüning et al., 2000), and the progressive establishment of a well
developed vegetation cover on the continents.
Previous studies have documented these latest Ordovician-Silurian
events in various areas of the planet, progressively evidencing
causative links between changes in the geosphere (variations in
global climate, carbon cycling, sea-level, surface-rock weathering,
sediment fluxes: e.g., Kaljo et al., 1988; Samtleben et al., 2000; Cramer
and Saltzman, 2005, 2007a,b) and perturbations in the biosphere
(faunal and floral extinctions, radiations, rates of biodiversity changes:
Jeppsson, 1987, 1990; Kaljo et al., 1995; Stricanne et al., 2006). This has
shown that the Silurian, once considered as a period of relatively

0031-0182/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.palaeo.2008.05.015
 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394 379

stable palaeoenvironmental conditions, was instead punctuated by
major instabilities in palaeoceanography, climate, carbon cycling on
time scales longer than 105 years (Samtleben et al., 2000; Munnecke
et al., 2003), as well as by extinction events in different fossil groups
(Kaljo et al., 1995; Munnecke et al., 2003). Isotopic investigations
coupled to detailed analysis of extinction patterns and fossil
biodiversity dynamics, have proved to be very useful for palaeoenvi-
ronmental reconstructions. A series of distinct excursions in oxygen
and carbon isotope values have been described (e.g., Munnecke et al.,
2003), which coincide with distinct lithological and biotic changes,

Fig. 1. Geographic location of borehole Tt1 in the context of main geological features of the Sahara Platform. Modified from Storch and Massa (2007).
380 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394

and seem to have global significance. However, most of the data
available on Silurian stable isotopic developments and patterns of
extinctions comes principally from Baltican and Laurentian localities
(Saltzman, 2002; Munnecke et al., 2003; Martma et al., 2005; Kaljo
and Martma, 2006; Cramer and Saltzman, 2007a,b).
The well preserved sedimentary sequences occurring in the
subsurface of North Africa represent an appropriate target in order
to provide the hitherto missing Gondwanan perspective of latest
Ordovician through Silurian environmental change.
In this paper, palynofacies and palynostratigraphic investigations
are combined with organic carbon isotope measurements of terminal
Ordovician through Silurian predominantly shaly sediments from the
northern Ghadamis Basin in the subsurface of southern Tunisia. We
provide the first carbon isotopic signal from Gondwanan Silurian
sedimentary sequences and couple it to coeval isotopic curves from
other areas. This enables us to set precise chronostratigraphic
constraints based on detailed fossil occurrences on the earliest to
early Silurian black shale units (e.g. “hot shales”) which has been a
somewhat controversial issue (cf., Lüning et al., 2000; Armstrong
et al., 2005, 2006; Lüning et al., 2006). In combination with the
observed palynofacies developments and changes in palynomorph
(mainly marine microphytoplankton and miospores) diversity we
shed more light on the origin of the Silurian black shales and the
environmental changes involved. The insights obtained contribute to
our global understanding of the evolution of life and its environment
during the Silurian.
2. Geological setting
Study material comes from a subsurface section in southern
Tunisia, in proximity of the Libyan border (borehole Tt1, Ghadamis
Basin; Fig. 1). This area is a part of the vast sedimentary zone which
crosses northern Africa between parallels 24 and 36° N lat, from the
Atlantic Ocean to the Red Sea, also known as the Saharan, or North
African, Platform. Vast and laterally continuous subcrops of Palaeozoic
sedimentary successions are known to occur over the greater part of
the Sahara Platform (Beuf et al., 1971). They are mainly developed into
large intracratonic basins, delimited by broadly elongated positive
structures showing a general north–south trend, and swinging
westward or eastward to the north (Balducchi and Pommier, 1970;
Beuf et al., 1971; Legrand, 1985). Palaeogeographically, North Africa
was located at the margin of Gondwana in high southern palaeola-
titudes (Fig. 2). The Lower Palaeozoic sedimentary successions of the
Sahara Platform are mainly detrital in nature, have not been affected
by metamorphism, and generally contain well preserved, often
thermally unaltered organic matter, including exceptionally well
preserved palynomorphs (acritarchs, chitinozoans, miospores; Jardiné
et al., 1974; El Arnauti et al., 1988; Paris, 1990; Vecoli, 2000). The
Ghadamis Basin is mainly developed in northwestern Libya, continu-
ing into southern Tunisia and eastern Algeria (Fig. 1), covering an area
of approximately 200.000 km2 (Massa, 1988; Rusk, 2001). The study
area, were borehole Tt1 is located, corresponds to a structural high
delimiting the northernmost extension of the Ghadamis Basin, known
as the Sidi-Toui uplift (“Môle de Sidi-Toui”; Massa, 1988, p. 39, Fig. 9),
which is the western continuation of the conspicuous Nefusah Uplift
of northeastern Libya (Figs. 1 and 2; Massa, 1988).
3. Borehole stratigraphy
The investigated core section ranges between −1330 m and −
1225 m core depth in borehole Tt1, spanning the latest Ordovician–
late Silurian (Ludlow) stratigraphic interval (Figs. 3 and 4). The
lithostratigraphic terminology adopted here follows the one defined
by Massa and Jaeger (1971), Jaeger et al. (1975), and Massa (1988) for
the Ghadamis Basin.
The lower part of the section, between ca. −1330 m and ca. −
1302 m consists of irregular alternations of fine-grained, immature
sandstones, siltstones and dark grey shales characterized by abundant
isolated angular to subangular quartz grains. These sediments are
considered to be of distal, peri-glacial origin and are attributed to the
Djeffara Formation (Jaeger et al., 1975; Massa, 1988). Recent
palynostratigraphic investigations of the widespread Ordovician,
glacial-related sediments over the entire Sahara Platform (e.g.,
“Argiles Microconglomératiques” in Algeria, the Djeffara Fm. in
Tunisia/NW Libya, the “2nd Bani” Fm. in Morocco), demonstrate an
Hirnantian age (latest Ordovician; Paris et al., 1995, 2000; Bourahrouh
et al., 2004; Ghienne et al., 2007; Vecoli, 2008). Three samples were
collected from this interval (Figs. 3 and 4).
Above the Djeffara Formation, a suite of fine grained, predomi-
nantly shaly to silty sediments with marly interbeds occurs. This

Fig. 2. Early Silurian palaeogeographic reconstruction (based on Scotese and McKerrow, 1990) with position of study area (open circle) and other localities documenting Silurian
isotopic events, as discussed in text. Numbers on map refer to several reports and multiple stratigraphic sections: 1 — North America (Laurentia; Saltzman, 2001; Cramer and
Saltzman, 2005; Cramer et al., 2006; Cramer and Saltzman, 2007a); 2 — Sweden (Baltica; Samtleben et al., 2000; Munnecke et al., 2003; Stricanne et al., 2006); 3 — Lithuania and
Estonia (Baltica; Martma et al., 2005; Kaljo and Martma, 2006); 4 — Australia (eastern Gondwana; Talent et al., 1993; Andrew et al., 1994); 5 — Prague Basin, Czech republic (peri-
Gondwana; Lehnert et al., 2007).
 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
381
Fig. 3. Lithostratigraphy, biostratigraphy, chronostratigraphic attributions, sampling levels in borehole Tt1, and stratigraphic occurrences of microphytoplankton species (acritarchs and prasinophytes).
382 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394

sedimentary succession is particularly rich in graptolites, which
permit reliable dating with a high degree of biostratigraphic precision,
indicating an age range from the early Llandovery to the Ludlow
(Jaeger et al., 1975; Massa, 1988). Based on several subcrop sections in
southern Tunisia and northwestern Libya, Jaeger et al. (1975) formally
named this early to late Silurian, silty–shaly succession as the “Argiles
Principales” Formation; distinguishing it from the broadly coeval but
clearly more proximal Tanezzuft Formation as defined in the outcrops
of the southern flank of the Murzuq Basin and to its corresponding
subcrops in southwestern Libya (Massa, 1988, Fig. 50).
The very base of the Argiles Principales Formation, in borehole Tt1
(−1302 m to −1298 m) is characterized by fine-grained sandstones
and quartzites with interbedded thin shale layers yielding graptolites
of the “vesiculosus” zone (Rhuddanian, early Llandovery: Jaeger et al.,
1975 and Storch, pers. comm., September 2007). From this interval,
five samples were available for analysis (Figs. 3 and 4).
Between −1298 m and −1267 m (thirteen samples collected; Figs. 3
and 4) a distinct interval occurs which is mainly composed of dark
grey to black shales and marls, rarely interbedded with limestone/
dolomite layers. Organic-rich black shales and shaly marls occur in
between −1298 m and −1280 m; these shales have TOC values varying
between 5% and 13% and are correlated to distinctly elevated Gamma-
ray values in the wireline log (Figs. 5 and 6), corresponding to the “hot
shales” definition (cf. Lüning et al., 2000). An interesting feature of the
hot shales in borehole Tt1 is the relatively high carbonate content,
which was also noted previously on the basis of the calcimetric well

Fig. 4. Stratigraphic occurrences of chitinozoans and miospores (cryptospores and spores triletes) in borehole Tt1, and previously established graptolite biozonation (Jaeger et al.,
1975).
 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
Fig. 5. Stratigraphic variation of δ13Corg and correlation with variation in relative γ-ray intensity (arbitrary unit) in borehole Tt1.
log data (Jaeger et al., 1975, Fig. 3). Although they were not directly
observed in the core samples analyzed for the present study, the
original lithological log of borehole Tt1 compiled by the drilling
company SEREPT reports the presence of dolomitic beds around −
1288 m. According to the graptolite data (Jaeger et al., 1975) but also to
new data from nearby boreholes (e.g., Lg3, St1; Storch, personal
comm., September 2007), the hot shale interval in borehole Tt1 as well
as in the adjacent wells in southern Tunisia contains at least the
sedgwikii graptolite Zone (Aeronian; Figs. 3 and 4). Moreover,
graptolites of the murchisoni and rigidus zones, indicating a Shein-
woodian (early Wenlock) age occur within and just above the Gamma
ray peak, between ca. −1278 m and −1287 m (Jaeger et al., 1975; Figs. 4
and 5). This clearly indicates that the southern Tunisian hot shales are
middle Llandovery to early Wenlock in age. However, no biostrati-
graphic evidence for the Telychian (late Llandovery) has found so far
in borehole Tt1, indicating a possible hiatus or highly condensed
sediments corresponding to this stage. The lundgreni graptolite Zone
(Homerian; late Wenlock) occurs in the uppermost part of the present
interval, near −1267 m (Jaeger et al., 1975).
Finally, the interval between −1267 m and −1224 m consists of a
monotonous succession of dark grey silty shales. A 20 meter-thick
383
interval (−1267 m to −1247.9 m) was not available for study from
borehole Tt1, but according to previous palaeontological analyses
(graptolites), it includes at least the vulgaris Zone of late Wenlock age
(Jaeger et al., 1975). The uppermost shaly interval ranging between −
1247.9 m and − 1225.2 m (six samples analyzed), has yielded
miospores and chitinozoans which indicate precisely a late Ludlow
(Ludfordian) age (Figs. 3 and 4). The Silurian sequence is truncated by
a major erosional surface at ca. −1224 m, above which sediments of
Late Permian age occur (Jaeger et al., 1975, and unpublished reports by
SEREPT oil company).
4. Analytical methods
The 27 samples available for study were treated for palynological,
palynofacies, organic carbon isotope, and Rock Eval analyses. Twenty
grams of sediments from each sample were dissolved in HCl and HF to
isolate the organic fraction. No oxidation was performed on the
organic residue. Organic carbon isotopic analysis was performed on
40–100 μg of the unfiltered organic-rich residue with an elemental
analyser (Carlo-Erba1110) connected online to a ThermoFinnigan
Delta Plus mass spectrometer, at the isotope laboratory of the Institute
384 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
Fig. 6. Stratigraphic variations of the TOC content and of the Rock-Eval parameters S2 and HI in core Tt1. Also indicated are the gamma-ray, for comparison with the TOC content, as
well as the interpretation of S2 values in terms of source rock potential.
of Geology and Mineralogy of the University of Erlangen, Germany. For
carbon isotope values, the conventional δ-notation in permil, relative
to V-PDB (Vienna-PDB) is used. For palynological and palynofacies
study, firstly one slide per sample was mounted using unfiltered
organic-rich residue, and subsequently the remainder of the residue
was filtered at 10 μm in order to eliminate the finer fraction of the
amorphous organic matter and facilitate the optical microscopy
analyses. Palynofacies analyses of 10-μm filtered residue is usually
recommended in the case of very organic-rich sediments (e.g., Batten,
1996), and this procedure was followed herein. For palynofacies
description and terminology, we followed Combaz (1964), Tyson
(1995), and Batten (1996). Three to nine palynological slides for each
sample were studied in order to reach a 250 palynomorph-count per
sample needed for standardizing the relative abundance calculations
of the different palynomorph groups. Additionally, residues from
samples particularly rich in organic-walled microfossils were also
filtered at 50 μm in order to isolate the larger palynomorphs from the
fine grained debris, and facilitate the taxonomic and biostratigraphic
study. Relative palynomorph abundance was estimated semi-quanti-
tatively on the basis of the relative number of palynomorph species
counted in one or more slides in order to reach the 250-specimen
count. Taking into account that all residues were obtained from the
same volume of sediment and that slides were mounted with an equal
amount of concentrated organic residue, this procedure is considered
to be sufficiently reliable to estimate the variations in relative
abundance of palynomoprhs per unity of volume of sediment
throughout the section (cf. De Vernal et al., 1987).
The total organic carbon content (TOC in weight %) was
determined on 100 mg of ground sediment sample with a Rock-Eval
instrument, Oil Show Analyser device (Espitalié et al., 1985a,b, 1986) at
the Université Paris 6, France. Other parameters given by the Rock-
Eval are the petroleum potential (S2 in mg HC per g of rock), the
hydrogen index (HI in mg HC per g of TOC) which depends on the
origin and state of preservation of the organic matter, and the Tmax
(°C) which is an indicator of thermal maturity of the organic matter.
5. Results
5.1. Palynology and palynofacies
All samples yielded palynomorphs in variable abundance and
diversity: acritarchs and prasinophytes (organic-walled marine
microphytoplankton), chitinozoans (marine microplankton), mios-
pores (dispersal propagules produced by early land plants) and, more
rarely, cryptospores were observed (Figs. 3 and 4; Plates I and II).
Detailed taxonomic evaluation of the various groups of palynomorphs
is not among the scopes of the present paper. Here only the major
features of the assemblages in relation to palynofacies characteristics
of the sediments, the palynomorph chronostratigraphic significance,
and their variation in relative abundance are presented and discussed.
The preservation of the various types of organic-walled micro-
fossils was variable, ranging from very good and light yellow colours of
vesicle walls, to medium and brownish colours (Plates I–III). No
opaque, completely carbonized palynomorphs were observed. An
exception is the preservation of acritarchs and chitinozoans in the
samples corresponding to sediments with the highest TOC values and
highest proportion of amorphous organic matter (AOM) which,
although presenting only slight thermal alteration, were highly
M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394 385

Plate I (caption on page 388).

386 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394

Plate II (caption on page 388).

 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
corroded on their surface, totally masking the microsculptural
elements and the fine branching of small appendices. Changes in
palynofacies type and relative abundance of the different classes of
sedimentary organic matter (SOM), closely correspond to the main
changes in palynomorph composition (Figs. 3, 4 and 8).
The palynofacies of samples 1330.0, 1313.6 and 1313.1 (uppermost
Djeffara Formation) are dominated by relatively well preserved, light-
coloured palynomorphs represented by abundant acritarchs, com-
monly occurring chitinozoans, and rare cryptospores (Figs. 3, 4; Plates
I and III). Amorphous organic matter (AOM) is subordinate, light in
colour, and badly preserved, showing signs of corrosion, probably due
to oxidation (Plate III, fig. 1).
The diverse acritarch assemblages, include the well known species
Acanthodiacrodium crassus, Leprotolypa evexa, Neoveryhachium carmi-
nae, Ordovicidium sp., Orthosphaeridium insculptum, O. rectangulare,
Villosacapsula villosapellicula, clearly indicating a Late Ordovician age
(Fig. 3; Plate I). Various species of large Baltisphaeridium also occur
which are consistent with this age attribution. Moreover, the presence
of Dactylofusa cucurbita, Deunffia sp., Hoegklintia sp., Saharidia
munfarida strongly supports a latest Ordovician (Hirnantian) age of
the sediments (Fig. 3; and cf. Vecoli and Le Hérissé, 2004; Vecoli,
2008). Acritarchs are generally well preserved, their walls being
transparent and pale yellow in colour. However, some minor signs of
corrosion of the wall are visible which may be attributed to slight
oxidation within the sediment (Plate I). Reworked acritarchs have
Plate III (caption on page 388).
387
been also observed, showing provenance from sediments of Middle
Ordovician age, such as species of Frankea and Dicrodiacrodium. These
reworked forms, although generally well preserved, are clearly
distinguishable from the in situ palynomorphs (apart from their age
difference with respect to the majority of the assemblage) by their
greater corrosion of the vesicle wall and incomplete/broken fine
appendages (Plate I, figs. 10, 12). The amount of reworked specimens
in the assemblages has been estimated to not exceed 2% of the total
palynomorph content. The presence of reworked palynomorphs has
been recorded repeatedly in Hirnantian, glacial-related deposits in
North Africa (Paris et al., 2000; Vecoli and Le Hérissé, 2004; Vecoli,
2008). Cryptospores also occur, albeit rarely (ca. 1% in relative
abundance), in this interval, indicating a relatively proximal character
of the sediments. Chitinozoans are infrequent and badly preserved
(mostly broken and with fine structures heavily corroded) so that they
cannot be identified at species level with certainty. Specimens of An-
gochitina sp., Belonechitina sp., Conochitina sp., Conochitina cf. elon-
gata, and Lagenochitina sp. were recorded. The chitinozoan
assemblage, although compatible with a Late Ordovician age, does
not permit to further refine the chronostratigraphic attribution
provided by the acritarchs in this interval.
The palynofacies type and palynomorph assemblages abruptly
change starting from sample 1301.5, at the base of the Argiles
Principales Formation (Rhuddanian; early Llandovery; Figs. 3, 4
and 8). Between −1301.5 m and −1294.0 m the dominant fraction of
388 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394

the palynological residue is AOM, and palynomorphs occur rarely and
are much less diverse than in the preceding interval. Acritarchs are
virtually absent and only very rare triangular Veryhachium spp. and
Evittia spp. were observed. These show dark yellow to brown vesicles
and corroded appendixes. Prasinophytes are also rare within this
interval, being represented by, Tasmanites, Leiosphaeridia and Cyma-
tiosphaera in decreasing order of abundance (Figs. 3, 4). In general,
abundances of acritarchs and of prasinophycean algae are inversely
correlated. The latter are much more abundant than the former
between −1297 m and −1282.0 m, the interval that corresponds to the
more organic-rich shales, with the highest values of natural radio-
activity (Figs. 3, 5, 8). An important fraction of the insoluble
palynological residue is constituted by pyrite, often occurring in
very fine framboidal aggregates. In all the basal part of the Argiles
Principales Formation (−1301.5 m up to −1267.0 m) AOM is relatively
well preserved (Plate III, fig. 2), dark yellow to brown in colour and
generally poorly fluorescent. It occurs abundantly in generally large
but dimensionally variable aggregates of extremely fine particles
clearly discernible under UV light. Observation in fluorescent light
also revealed, in some specific levels, a significant number of
palynomorphs within the groundmass of the more densely aggre-
gated particles which appeared semi-opaque at their centre upon
optical microscopy observation (Plate III, fig. 4). Neither structure, nor
remnants of possible pre-existing structures are detectable even if
observed in fluorescent light.
The interval between − 1291.1 m and − 1267 m is richer in
palynomorphs; acritarch assemblages here are better preserved and
dominated by species of Ammonidium (e.g., Ammonidium microcla-
dum), and, secondarily, of Tylotopalla and Leiofusa. Tylotopalla is often
represented by aberrant forms showing few, heteromorphic processes
irregularly distributed on vesicle surface. An acritarch diversity peak is
observed at −1291.1, where species of Oppilatala, Multiplicisphaeri-
dium, and Leiofusa occur. The diversity of acritarch assemblages and
palynomorph vs. AOM relative abundance slightly increase again in
samples 1273.0, 1270.5, reaching a further peak at −1267.0 m, were
numerous acritarch taxa first occur (Fig. 3). At this level, the
prasinophyte assemblage is also more diverse than in stratigraphically
lower levels, due the inception of species of Dictyotidium, Quadrati-
tum, and Duvernaysphaera. The precise chronostratigraphic signifi-
cance of the phytoplankton assemblages recovered from the interval
between −1301.5 m and −1267.0 m is difficult to evaluate because the
exact stratigraphic ranges of many species are still poorly known.
However, a general agreement with the biostratigraphic ages provided
by the graptolites is evident. In particular, the species Ammonidium
microcladum, Oppilatala sp., Tylotopalla sp., Quadraditum fantasticum
are consistent with an early to middle Silurian (Llandovery–Wenlock)
age.
Chitinozoans occur in generally low but constant abundances
throughout the stratigraphic interval between −1301.5 m and −
1267.0 m, and show variable preservation from highly corroded to
well preserved vesicles. The following stratigraphically significant
species have been observed (Fig. 4): Spinachitina fragilis (which is an
index species for the basal Rhuddanian) occurs at −1301.5 m. Spina-
chitina maennili and Conochitina edjelensis edjelensis are present
between − 1296.0 m and − 1288.35 m thus indicating a latest
Rhuddanian–middle Aeronian age. Angochitina longicollis, whose
known stratigraphic range is from Telychian −lower Sheinwoodian,
occurs at −1286.9 m. The above chitinozoan datings are based on the
synthetic chitinozoan range chart for the Silurian compiled by Paris
(1996) and on data from the global Silurian chitinozoan zonation

Plate I. Latest Ordovician acritarchs and cryptospore (sample Tt1-1313.1). Scale bar equals 10 μm. (see page 385)

Fig. 1. Multiplicisphaeridium sp.

Fig. 2. Acanthodiacrodium crassus (Loeblich and Tappan, 1978) Vecoli, 1999.
Fig. 3. Veryhachium lairdii (Deflandre) Deunff, 1959 ex Downie, 1959.
Fig. 4. Cryptospore.
Fig. 5. Dactylofusa striatogranulata Jardiné et al. (1974).
Fig. 6. Leprotolypa evexa Colbath, 1979.
Fig. 7. Multiplicisphaeridium sp.
Fig. 8. Deunffia sp.
Fig. 9. Villosacapsula setosapellicula (Loeblich) Loeblich and Tappan, 1976.
Fig. 10. Dicrodiacrodium ancoriformis Burmann, 1968 emend. Servais et al., 1996⁎.
Fig. 11. Quadruilobus spinatus Tappan and Loeblich, 1971.
Fig. 12. Frankea sartbernardensis (Martin) Colbath, 1986⁎.

Plate II. Chitinozoans, miospores and acritarchs of Ludlow (late Silurian) age (samples Tt1-1247.9 and Tt1-1225.2). Scale bar equals 10 μm. (see page 386)

Fig. 1. Angochitina echinata Eisenack.

Fig. 2. Cingulochitina sp. A of Paris, 1981.
Fig. 3. Ancyrochitina primitiva Eisenack.
Fig. 4. ?Archaeozonotriletes sp. cf. A. divellomedium Chibrikova, 1959.
Fig. 5. cf. Synorisporites verrucatus (Richardson and Lister) Richardson and Ioannides, 1973.
Fig. 6. Ambitisporites avitus Hoffmeister, 1959.
Fig. 7. Baltisphaeridium sp.
Fig. 8. Dateriocradus polydactylus Tappan and Loeblich, 1971.
Fig. 9. Neoveryhachium carminae (Cramer) Cramer, 1971.
Fig. 10. Oppilatala sp. cf. O. eoplanktonica (Eisenack) Dorning, 1981.
Fig. 11. Evittia remota (Deunff) Lister, 1970.
Fig. 12. Leiofusa algerensis Cramer, 1970 ex Eisenack et al., 1976.

Plate III. Palynofacies of latest Ordovician and Silurian sediments in borehole Tt1. Scale bar equals 50 μm in Figs. 1–3, and 10 μm in Figs. 4–12. (see page 387)

Fig. 1. Palynofacies of sediments from uppermost Djeffara Formation, latest Ordovician (sample Tt1-1313.1). Note well preserved and abundant acritarchs, subordinate
AOM, light in colour and badly preserved.
Fig. 2. Palynofacies of sediments from the “hot shale” interval in the Argiles Principales Formation, Aeronian, Middle Llandovery (sample Tt1-1291.1). Note extreme
abundance of well preserved, structureless AOM.
Fig. 3. Palynofacies of sediments from the upper part of the Argiles Principales Formation, late Ludlow (sample 1240.5). Note well preserved and diversified palynomorph
assemblages, including acritarchs and miospores, and subordinate AOM.
Fig. 4. Fluorescent light view of structureless, partly fluorescent well preserved AOM from the “hot shales” interval in borehole Tt1 (sample Tt1-1291.1), revealing highly
fluorescent acritarch completely embedded within large AOM aggregate, and indiscernible under normal light microscopy observation.
 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394 389

proposed by Verniers et al. (1995); they are in remarkable agreement

with the ages inferred from graptolites.
A further marked change in the palynomorph composition and
palynofacies type occurs at −1247.9 m, characterizing the rest of the
stratigraphic section, up to − 1225.2 m just below the major
unconformity surface. In this interval, abundance of palynomorphs
increases again, while the amount of AOM is reduced (Plate III, fig. 3).
One of the most striking features is the abundant occurrence of land-
derived organic debris and palynomorphs (miospores) which repre-
sent ca. 30% of the total palynomorph content (Fig. 8). Several
cryptospores and trilete spores species are present, of which the most
abundant and biostratigraphically significant are Ambitisporites avitus,
?Archaeozonotriletes sp. cf. A. divellomedium, Laevolancis divellome-
dium, Retusotriletes warringtoni, and Synorisporites verrucatus, and
Emphanisporites rotatus. The co-occurrence of these taxa permits to
identify the Synosporites lybicus – Chelinospora poecilomorpha Zone,
spanning the late Gorstian – Ludfordian time interval. Acritarchs are
represented by well preserved and diversified assemblages, including
some long-ranging taxa (Late Ordovician – Silurian) species such as
Evittia remota (sensu “Baltisphaeridium denticulatum complex” of
Cramer, 1970); Neoveryhachium carminae, various species of Balti-
sphaeridium, but also some taxa characteristic of middle-late Silurian
age, such as species of Visbysphaera, Oppilatala, Triangulina, Tuni-
sphaeridium. Other taxa have more restricted stratigraphic ranges,
Fig. 7. Plot of HI vs Tmax values for core Tt1 (diagram from Espitalié et al., 1986). Symbols
such as Deflandrastrum millepiedi and D. leonardi, which permit to
as in Fig. 6.
tentatively restrict the age range of the assemblage to the late Ludlow
(Ludfordian; e.g., Cramer, 1970), further refining the biostratigraphic
age provided by the miospore assemblage.
Well preserved and relatively diversified chitinozoans are also excursions evidencing three maxima at −1294 m (+2‰ positive shift;
present, including the chronostratigraphically significant species An- hot shale interval; early Aeronian, middle Llandovery), at −1286.9 m
cyrochitina primitiva, Angochitina echinata (Plate II, Figs. 1, 2), Cingu- (+2.5‰ positive shift; hot shale interval; Llandovery/Wenlock bound-
lochitina cf. convexa, and Sphaerochitina acanthifera, well compatible ary or earliest Wenlock), and at −1240.5 m (+3‰ positive shift; shaly
with the late Ludlow age suggested by acritarch evidence (Verniers level within the predominantly silty upper portion of the Argiles
et al., 1995; Paris, 1996). Principales Formation, Ludfordian, late Ludlow). The minimum values
are mostly concentrated in the lower part of the section, correspond-
5.2. Toc and rock-eval ing to the poorly sorted sandstones and silts of the Djeffara Formation
(latest Ordovician) and to the fine grained sandstones at the base of
The TOC values range between 0.2 and 13.2% (Fig. 6). The vertical the Argiles Principales Formation (earliest Llandovery). In addition,
distribution of TOC values is clearly correlated with the Gamma-ray very low δ13Corg are also recorded in a short interval just above the hot
curve (Fig. 6). Very low TOC values (average 0.4%) are observed in the shale package within the Argiles Principales Fm. (Wenlock). A much
Hirnantian sediments of the Djeffara Formation, between −1330 m less pronounced and more gradual excursion (+1‰ positive shift;
and −1313.1 m. An increase is noted at the transition with the Argiles maximum δ13Corg value −29.83‰) is also observed at −1273 m
Principales formation which is generally characterised by high TOC (possibly middle Wenlock; Sheinwoodian/Homerian transition). An
values (5.6%). Maximum TOC values identify the hot shale interval isolated, relatively high δ13Corg value (−28.87‰) finally occurs at the
(−1298 m to −1280 m). A return to relatively low TOC values is topmost level of the study section, only a few tens of centimetres
observed in the Ludlow silty shales (average 1.4%), except at − below the conspicuous discontinuity surface at −1224 m.
1240.5 m, where TOC values up to 2.9% are recorded (Fig. 6).
Tmax values range between 428 and 443 °C (Fig. 7), with an average 6. Discussion
of 437 °C. These values indicate that the organic matter has just
reached the beginning of the oil window. The present data evidence remarkable correlation between
The type-and therefore the origin- of the organic matter present palaeontological, palynofacies, isotopic, and lithological develop-
can be determined using the HI-Tmax diagram (Fig. 7; Espitalié et al., ments throughout the study section (Figs. 3–8). Palynofacies of the
1986). Within this diagram, most of the samples plot in the lower part Hirnantian sediments of the Djeffara Fm., showing low abundances of
of Type II organic matter while a few samples plot in the Type III part highly degraded AOM, suggest a well oxygenated environment; this is
of the diagram. also well supported by organic geochemistry data (low TOC and HI
Consistent with the high TOC values and relatively low thermal values). Moreover, the high diversity of the acritarch assemblage
maturity of the samples, a high petroleum potential (S2) is observed in indicates normal marine, oligotrophic conditions, relatable to outer
most of the samples of the Argiles Principales Formation which rates shelf palaeoenvironmental setting. In the literature, the Hirnantian
as good to very good petroleum source rock. Conversely, the sediments of the “Argiles microconglomératiques”-type are often
Hirnantian Djeffara Formation and the Ludlow silty shales only considered of peri-glacial nature, deposited mostly during the melting
show poor to fair source rock potential. of the Gondwanan ice-cap (Paris et al., 1995, 2000), which is
consistent with well oxygenated and normal marine environment of
5.3. Stable carbon isotopes deposition. The low isotopic values recorded in the three samples
analyzed in this interval (Fig. 5) possibly indicate a late Hirnantian
In the Tt1 core (Fig. 5), a baseline of low δ13Corg values varying time (i.e., post- early Hirnantian isotopic excursion), and thus are also
between −30.79 and −30.59‰ is interrupted by three distinct positive consistent with this scenario.
390 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
Fig. 8. Stratigraphic variations of palynofacies type, relative abundance of main classes of palynomorphs, and diversity of marine microphytoplankton.
There is no evidence of major discontinuities at the Ordovician/
Silurian transition in the study section, even if the sequence is very
condensed (Figs. 3 and 4); this is clearly substantiated by the presence
of Rhuddanian (earliest Silurian) graptolites (vesiculosus Zone)
between −1300.4 m and −1301.7 m and chitinozoans (fragilis Zone)
at −1300 m, a few meters above the last occurrence of Hirnantian
(latest Ordovician) palynomorphs (Figs. 3 and 4). The distinct
lithological change marking the boundary between the Djeffara and
Argiles Principales formations (ca. −1302 m; Fig. 3) coincides with a
first important change in palynofacies type and turnover of the
palynomorph assemblage (Fig. 8). The basal portion of the Argiles
Principales Formation (−1302 m to −1298 m) is characterized by
palynofacies dominated by slightly degraded and essentially non-
fluorescent AOM, by a drastic reduction in diversity of the acritarch
assemblage and by an increase in occurrence of prasinophyceae (Figs.
3 and 8). TOC values increase markedly, but values of HI as well as δ13C
values remains low and similar to the values recorded in the
Hirnantian sediments of the Djeffara Fm. (Figs. 5–8). Globally, these
characteristics suggest an increase in productivity, although palaeoen-
vironmental conditions were not particularly favourable to preserva-
tion of organic matter. Two possible scenarios can be envisaged to
explain this situation. A first possibility is that the increase in
bioproductivity was still not strong enough to cause complete anoxia
within the sediment which only reached a dysoxic state, permitting
only partial preservation of OM. Alternatively, anoxia was effectively
developed within the sediments, but the sea level was shallow enough
to keep the sediment/water interface above the average storm wave
base, which would have caused periodical remixing and oxygenation
of the sediment. This possibility seems supported by the presence of
silty to sandy cm-thick layers within a predominantly shaly succes-
sion, but also by the low values of the HI index of the OM (Figs. 3
and 7). It should be borne in mind that this basal interval of the Argiles
Principales Fm. is Rhuddanian in age, meaning that is was being
deposited while in the deeper parts of the Ghadamis Basin (but also in
other basins in adjoining areas; Fig. 1) extensive black shale deposition
was already active and thus anoxic conditions were widespread across
the entire Sahara Platform (Lüning et al., 2000).
The base of the hot shale interval, at −1298 m, marks a second well
defined change in palynofacies, petrological, and organic geochemical
parameters (Figs. 3–8). In the palynofacies spectrum, a further
increase in abundance of AOM is recorded. Hot shale AOM still
appears as featureless aggregates of very fine particles (≤1 μm in
diameter), but shows more elevated fluorescence, suggesting
enhanced preservation of organic matter (cf. Tyson, 1995). Increased
values of HI and exceptionally high TOC values (consistent with the
increased fluorescence of the AOM; Tyson, 1995, 2006) coupled to
elevated levels of natural radioactivity (Figs. 6 and 7) also indicate
better preservation of AOM, thus suggesting the establishment of full
 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
anoxic conditions within the sediments. The low diversity of the
acritarch assemblages, associated to an increase in the abundance of
prasinophyceae algae, strongly support enhanced surface bioproduc-
tivity and establishment of eutrophic conditions in surface oceanic
waters (Combaz, 1966; Revill et al., 1994). According to Lüning et al.
(2000), conditions of strong upwelling all along the margin of
Gondwana at high latitudes were at the origin of extensive organic-
rich black shales deposits in large parts of the Sahara Platform, the
middle East and in the Arabian Peninsula. The present results are in
agreement with a scenario of upwelling-triggered high surface
productivity and anoxia in the water column and in the bottom
sediments for the origin of the Tunisian hot shales. It should also be
noted, that the abundance of prasinophyceae may indicate prolifera-
tion in upwelling nutrient-enriched waters (Revill et al., 1994). The
observed offset in hot shale depositional age (younger on palaeo-
highs, older in basin palaeo-depressions) might be well explained by
deposition of organic-rich sediments during a marine transgression,
as postulated also by Lüning et al. (2000). Such temporal changes in
the location of upwelling-derived organic-rich sediments in parallel to
sea level variations have been well documented in recent situations
(Mollenhauer et al., 2002). The hot shale interval is also characterized
by two distinct isotopic excursions, one occurring in levels dated as
Aeronian (middle Llandovery) and the other, more pronounced,
occurring in levels dated as Sheinwoodian (basal Wenlock; Fig. 5).
Early to middle Silurian isotopic excursions are well known in
carbonate sequences from many low palaeolatitude settings (Laur-
entia and Baltica), where they are often associated to faunal
extinctions and lithological changes (see Munnecke et al., 2003 and
Cramer and Saltzman, 2007a, for a review). One of the most studied of
these isotopic events is the pronounced early Sheinwoodian (earliest
Wenlock) excursion, associated with the so-called “Ireviken Event”
(Jeppsson, 1987, 1990, 1993, 1997; Munnecke et al., 2003; Cramer and
Saltzman, 2005; Kaljo and Martma, 2006; Cramer and Saltzman,
2007a,b; Loydell, 2007). This event appears to be global in character,
as it has been recorded in several areas (Fig. 2), especially in equatorial
to tropical latitude settings such as North America (Saltzman, 2001;
Cramer and Saltzman, 2005; Cramer et al., 2006; Cramer and
Saltzman, 2007b), the Baltic region (Kaljo et al., 1997; Munnecke
et al., 2003; Martma et al., 2005), and Australia (Talent et al., 1993).
Although Silurian carbonate deposits are not extensively present in
the Ghadamis Basin, major global palaeoenvironmental disturbances
should be detectable in the isotopic signature of the sedimentary
organic carbon. Previous studies have in fact clearly demonstrated
that if variations in δ13C are the expression of changes in carbon
cycling at a global scale, not only are they detectable in both inorganic
and organic carbon species, but also show the same variation polarity
(Strauss et al., 1997; Hayes et al., 1999). Principally because of its
stratigraphic position, precisely established in early Sheinwoodian
times, the more pronounced and stratigraphically highest of the two
isotopic excursions observed in the hot shale interval in borehole Tt1,
might represent the record of the “Ireviken Event” in the study area.
An isolated peak in acritarch diversity is recorded in one sampling
level about 4 m below the isotope peak, but the significance of this
diversity fluctuation is difficult to evaluate because of the generally
very low abundance of acritarchs in these levels. In the Baltic regions,
the Ireviken Event is usually preceded by at least two minor isotopic
excursions in δ13Ccarb, of Aeronian and Telychian time, respectively
(Munnecke et al., 2003). Consistently, the early Sheinwoodian
excursion is preceded in the Tt1 section, by a smaller excursion
dated as middle Llandovery (Aeronian), while the absence of a
Telychian excursion may be well explained in our case by the hiatus
embracing the major part, if not the entirety of the upper Llandovery
(Figs. 3–5). These results are apparently in contrast with the recent
study by Cramer and Saltzman (2007b) who described a trend
towards more negative δ13Corg values through the Ireviken event in
the North American Midcontinent. However, in our opinion, the
391
δ13Corg data presented by Cramer and Saltzman (2007b, Fig. 4) do not
depict an evident negative excursion, but rather seem to be scattered
over a wide range of values. More isotopic data on organic carbon will
be needed in order to verify and correctly interpret the apparently
divergent isotopic signatures in the different species of carbon as
presented by Cramer and Saltzman (2007b). For the scope of the
present discussion, we will therefore assume that our δ13Corg
excursion effectively records the high-latitude expression of the well
known excursion which correlates with the Ireviken Event. Therefore,
our data can be discussed in the light of the oceanographic and
climatic models proposed to account for the observed changes in the
Silurian isotopic, sedimentary, and fossil records (Jeppsson, 1987,
1990, 1993, 1997; Munnecke et al., 2003). Recently, Cramer and
Saltzman (2007a), presented a review of these models, with a new
proposal which has been developed in order to explain the apparent
contradiction between increased levels of organic carbon burial
required to explain the positive isotopic shift of the Ireviken Event,
and the widespread development of carbonate platforms in low
latitudes during early to middlle Silurian times. These authors
suggested that the Ireviken Event developed during a time of
decreasing levels of primary productivity in epeiric seas due to a
large transgression linked to the demise of a late Llandovery
glaciation. At the transgression peak, a climatic warming would
have caused not only a shift from estuarine to anti-estuarine
circulation in epeiric seas favouring the development of carbonatic
factories, but also a change in the site of deep water formation from
high- to low-latitude setting, with consequent development of anoxia
in the oceanic deeper basins. The decoupling between carbonatic
epicontinental platforms and the deep anoxic oceans (sites of
sequestration of isotopically light carbon) would largely explain why
the early-middle Silurian isotopic excursions are found to occur during
intervals of increased carbonate production.
In the Tt1 section, palaeogeographically located on a basin-margin
palaeohigh, the main isotopic peak (at −1286.9 m) occurs within the
hot shale interval, near its upper end. It is then followed by a return to
organically leaner silts and shales, probably meaning that the bulk of
organic matter burial actually took place in high latitude settings
slightly before the onset of the “Ireviken” isotopic excursion. This is
especially clear considering that in the deeper parts of the Gondwanan
intracratonic basins, hot shale deposition occurred significantly earlier
than on basin margins (in Rhuddanian, early Llandovery times). It
must be noted also that the occurrence of thin dolomitic layers
interbedded within the Tunisian hot shales such as around −1288 m in
borehole Tt1, may be a consequence of the large availability of Ca and
Mg during this time interval. The apparent absence of Telychian
sediments in the Tt1 section (Figs. 3 and 4) might be in agreement
with a climatically (glacially?) driven sea level lowstand in late
Llandovery times, as postulated by Cramer and Saltzman (2007a), but
obvious direct evidence of a middle Silurian glaciation is lacking in our
section and generally in North Africa. Additionally, the present results
prove that important volumes of highly organic-rich sediments were
effectively deposited in Gondwanan high latitude intracratonic
shallow seas during an extended period of time from basal Llandovery
to basal Wenlock. This evidence partly contradicts Cramer and
Saltzman (2007a) assertion that the Ireviken excursion is associated
with a “decrease in organic carbon burial in shallow water globally”.
A progressive return to lower productivity and less anoxic
conditions after the end of hot shale deposition is suggested in
borehole Tt1 by increasing diversity of the microphytoplankton
assemblages accompanied by decreasing abundance of poorly
fluorescent AOM as well as decreasing TOC (and δ13Corg values) in
the interval between −1278.6 m and −1267.0 m (Figs. 3 and 7). This
stratigraphic interval shows similar characteristics, and might some-
how reflect comparable palaeoenvironmental conditions of the basal
part of the formation, between −1302 m and −1298 m, though still
generally high HI values testify to a relatively good preservation of OM.
392 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
This decrease in surface productivity could parallel the documented
3rd (2nd?) order sea-level fall occurring in the upper Wenlock (Lüning
et al., 2000).
The upper part of the section is characterized by a large positive
excursion in δ13Corg, which coincides with a slight increase in TOC
within an interval of generally low TOC and low HI values (−1247.9 m
to −1225.2 m; Figs. 5 and 7). The associated palynofacies shows
abundance of palynomorphs (miospores, prasinophytes, acritarchs
and chitinozoans) and an essentially non-fluorescent AOM. The
acritarchs are in general relatively abundant and diverse (Fig. 3),
suggesting conditions of normal marine platformal environment
throughout this interval. A marked decrease in acritarch diversity is
recorded starting at −1243.0 m, immediately before the carbon
isotopic maximum (Figs. 5 and 8). A distinct change in the
composition of the acritarch assemblages is associated with this
diversity decline (Figs. 3 and 8). Post-excursion acritarch assemblages
are not only less diverse, but are largely dominated by a few species
belonging to the genera Evittia, Neoveryhachium, and by triangular
Veryhachium, with the other taxa represented by very rare occur-
rences. Miospores show an evident increase in abundance in parallel
with the increasing values of δ13Corg, reaching a maximum in
correspondence of the isotope peak, where they make up ca. 30% of
the total palynomorph content. The geochemical as well as palyno-
facies parameters can be interpreted as to indicate oligotrophic
conditions of the surface waters and well oxygenated bottom
sediments. The marked isotopic excursion at −1240.5 m falls in a
stratigraphic interval which is dated as late Ludlow based on acritarch,
chitinozoan and miospore evidence (Figs. 3–5). A major late Silurian
(late Ludlow, Ludfordian) isotopic excursion is well known from many
localities of low palaeo-latitudes (Fig. 2) in Baltica (Sweden and Baltic
States: Samtleben et al., 1996, 2000, Martma et al., 2005), Laurentia
(North America: Saltzman, 2001), and eastern Gondwana (Australia;
Andrew et al., 1994; Jeppsson et al., 2007), as well as from one middle
palaeo-latitude peri-Gondwana locality of the Prague Basin (Lehnert
et al., 2007). This prominent excursion is correlated to lithological and
faunal changes in many sections worldwide and it is generally
associated to an oceanic event named the “Lau Event” (see recent
review in Martma et al., 2005). Although the precise age of the
excursion is currently debated between a middle or late Ludfordian
(late Ludlow) age (Kaljo and Martma, 2006; Lehnert et al., 2007), there
is little doubt that the large isotopic excursion occurring in the upper
part of the Tt1 section (broadly dated as late Ludlow) is correlatable to
the Lau Event.
As with the other Silurian excursions, the Lau Event has been
related to changes in palaeoclimatic conditions (Martma et al., 2005;
Lehnert et al., 2007), switching from a humid to an arid state.
Interestingly, a recent detailed study which included analyses of
palynological changes across the Lau event in Sweden (Stricanne et al.,
2006) recorded a peak in abundance of miospores in correspondence
of the carbon isotope peak, similarly to what observed in borehole Tt1.
In the latter study, acritarch abundance was anti-correlated with
miospore abundance and this was taken as an indication of decreasing
levels of primary production in the photic zone. The input from
terrestrial plant sources (the miospores) was explained by Stricanne
et al. (2006) as due to aeolian transport because other possible
explanations (sea-level drop or instauration of humid climate) were
not supported by sedimentological and isotopic (e.g., δ18O) evidence.
On the basis of the available data, we are not able either to confirm or
reject this hypothesis, because lithological and sedimentological
indicators of climatic conditions are not obvious in the predominantly
fine-clastic sedimentary sequence studied by us (not continuously
cored). However, integrating the geochemical and palynofacies
evidence, it is possible to infer “normal” conditions of palaeoproduc-
tivity as well as oxygenated bottom sediments, moderately favourable
to preservation of organic matter. The relationships between acritarch
abundance in the sediments and levels of primary production in the
water column are very difficult to evaluate, because: 1) it is possible
that microphytoplankton did not produced cysts during specific
environmental conditions; 2) the absolute abundance of cysts per unit
of volume of sediments is strongly dependent by hydrodynamic
factors prevailing during deposition; 3) possibility of selective post-
diagenetic degradation/preservation of organic cysts within the
sediment. Tongiorgi et al. (2003), for example, showed that the
number of acritarchs per gram of rock in Middle Ordovician strata of
the Yangtze Platform, China, was strictly controlled by lithology, and
that no definite meaning could be attached to the distribution of
palynologically barren samples. The present results show, however, an
evident similarity with the observations made by Stricanne et al.
(2006) on compositional changes of acritarch assemblages across the
Lau event at Gotland, Sweden in that a major acritarch turnover is
recorded to occur during the increase in isotopic values (Figs. 3, 5
and 8). However, the dominance of acritarchs with short, non–
ramified processes in correspondence of the late Ludfordian excursion
which characterizes the Swedish acritarch assemblages at Gotland
(Stricanne et al., 2006) was not observed in the present study. This
might reflect different palaeobiogeographic settings (low versus high
palaeolatitudes) of the two areas.
The recorded input of miospores in the Tt1 borehole reflects two
concurrent factors: one is the evolution of early land plants, with a
progressive increase in geographical diffusion, biological complexity
and diversity of spore-producing plants during the critical Silurian
time interval. The second factor is the progradation of shallow and
marginal marine deposits into more basinal areas during a second-
order regression observed regionally over the entire North Africa (HST
of sequence NA2 of Carr, 2002). At the present state of knowledge, it
would be premature to speculate about palaeoclimatic variations
(humid vs. arid conditions) based on the spore assemblages. The
occurrence of relatively abundant miospore content in the palynolo-
gical residues is not likely to have a significant influence on the carbon
isotopic signal, as it might be inferred from the apparent correlation
between the δ13C Ludfordian peak and the maximum in miospore
abundance at 1240.5 m (Figs. 4 and 8). Differences in the δ13C between
Silurian marine palynomorphs (acritarchs and prasinophyte algae)
and terrestrially derived woody fragments of Devonian age were
documented by Lécuyer and Paris (1997). These authors measured
significant differences, up to 4‰, between the carbon isotopic ratio of
land plant derived woody fragments and marine algae, although these
were measured in specimens extracted from samples of different age
and localities. In our material, at the maximum abundance, miospores
contribute for the 30% of the palynological content, 60% of it being of
marine derivation (phytoplankton). In addition, the bulk of the
organic residue (60%) is constituted of amorphous organic matter of
marine origin (derived either from bacterioplankton or degraded
phytoplankton). Lécuyer and Paris (1997) calculated that 25% of
woody tissue in an organic residue would modify the δ13C value of the
sediment by 1‰. Accordingly, a significant effect on the carbon
isotopic fractionation curve would be expected only if woody
fragments occurred abundantly in the palynological residue, as it
has been effectively observed in sediments of Devonian age
(Joachimsky, pers. comm., February 2008). However, in our study
samples, woody fragments are absent, and only miospores occur in
maximum abundance of ca. 15% of the total organic residue. Miospores
are mostly very thin-walled (1–2 μm), spherical vesicles which are
empty internally, and thus contribute much less towards the total
mass of atoms of C per unit of volume than woody fragments.
The difficulty of explaining the driving mechanisms of the Lau
Event and associated isotopic excursion with the same oceanographic
models proposed for the early to middle Silurian events (e.g., the
Ireviken event) was recently highlighted by a new detailed study of
late Ludfordian sediments from Gotland, Sweden (Eriksson and
Calner, 2008). These authors proposed two possible mechanisms for
the late Ludfordian isotope excursion: 1 — a glacio-eustatically
 M. Vecoli et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 378–394
induced increase in weathering rate due to lowered sea level causing a
change in the riverine C-weathering flux towards enriched δ13C values
("weathering hypothesis" of Kump et al., 1999); and 2 — an increased
photosynthetic activity by benthic cyanobacteria causing enrichment
in δ13C in precipitating carbonates. It is interesting to note that the
miospore abundance peak we observe at the Lau event would be a
consequence of the former scenario and not of the latter.
The isotopic excursions recorded here have generally smaller
amplitudes than those corresponding to the same events but
measured in carbonatic sections elsewhere. This is particularly
evident for the Ludfordian (Lau) excursion, which in the literature is
described as having an average amplitude between 8–9‰, exception-
ally reaching 10‰ δ13C. In comparison, our reported Ludfordian
excursion of about 3‰ δ13C is significantly smaller. A trend towards a
basinward decline in the magnitudes of positive δ13C excursions has
been previously described in the literature (e.g., Kaljo et al., 1997;
Noble et al., 2005; Melchin and Holmden, 2006), and was discussed
more in detail by Loydell (2007) for the early and middle Silurian
excursions. The early Sheinwoodian (Ireviken) excursion in borehole
Tt1 has similar magnitude as, for example, the one recorded by Kaljo
et al. (1997) in relatively deep water facies in Latvian localities. The
graptolite-rich, fine-grained early Wenlock sediments of borehole Tt1
are compatible with a distal platformal depositional setting, as
previously noted by Jaeger et al. (1975), and this could easily explain
the slightly smaller amplitude of the recorded early Sheinwoodian
excursion. A similar argument can be advanced to explain the reduced
magnitude of the Ludfordian excursion in borehole Tt1. Even if the
excursion falls during a time of a prevailing, second order, regressive
trend, the late Ludlow depositional setting of section Tt1is still a
relatively distal one (Jaeger et al., 1975). Possibly, an additional factor
might be that as a result of the discontinuous sampling across the
excursion interval, the exact stratigraphic level corresponding to the
peak of the curve may have been missed.
7. Conclusions
1. In the present study, we have analyzed the relationships between
lithological changes, fluctuations in biodiversity of marine micro-
phytoplankton, changes in oceanic productivity, development of
anoxia, and organic carbon isotopic excursions in latest Ordovician
through Silurian clastic sequences of the high-latitude regions of
Gondwana.
2. The two major early Sheinwoodian (basal Wenlock) and Ludfordian
(late Ludlow) carbon isotope positive excursions, which are thought to
reflect global palaeoceanographic changes and are associated to biotic
events (Ireviken and Lau event, respectively), have been identified for
the first time in Gondwanan high-latitude settings (North Africa).
3. Our data demonstrate that an extended period of black shale
deposition occurred regionally (even if discontinuously in geo-
graphic extent) over the entire North African margin from
Rhuddanian to early Wenlock times. The palynofacies and organic
geochemical evidence support an origin by coastal upwelling-
promoted productivity increase. The landward shift in location of
coastal upwelling following a long-term (second order?) transgres-
sion might explain the observed pattern of black shale deposition
and is also well in accordance with a previous model of early
Silurian black shale deposition on the North African craton,
previously proposed by Lüning et al. (2000).
4. Accordingly, the isotopic shift associated with the Ireviken event
occurred during the later phases of a protracted period of massive
black shale deposition, and thus of organic carbon burial, on
continental platforms located in high-latitude settings. This could
well explain the apparent contradiction between carbonate deposi-
tion and carbon isotopic shift towards lighter values widely observed
in low latitude areas (North American Midcontinent, Cramer and
Saltzman, 2005, 2007a,b; Baltic regions, Munnecke et al., 2003).
393
5. The Lau event is more difficult to interpret. Extensive black shale
deposition does not occur in association with this event, and levels
of primary productivity seem to have remained essentially
unchanged before and during the event (oligotrophic conditions
as suggested by palynofacies evidence). An input of organic matter
of terrestrial derivation into the marine sedimentary record
(miospores of early land plants) correlate exactly with the
maximum values of organic carbon isotopic fractionation, similarly
to what has been observed in the Baltic region (Stricanne et al.,
2006).
6. Our study demonstrate that previous models developed in the low
to intermediate palaeolatitude settings to explain the observed
association among isotopic development, facies changes, and
fluctuation in biodiversity, cannot be readily applied in the more
general case, and particularly in the case of high-palaeolatitude
localities. More detailed investigation from different Gondwanan
localities will be needed in order to enlarge the dataset and
improve our knowledge of the Silurian global palaeoceanographic
events.
Acknowledgements
The study material, including original borehole logs, was provided
by Dominique Massa. This study is a contribution to the project
“ECLIPSE II: The Terrestrialization process: modelling complex inter-
actions at the geosphere–biosphere interface”; financial support by
the CNRS and INSU is gratefully acknowledged. François Baudin and
Florence Savignac (Université P. et M. Curie, Paris 6) are thanked for
performing the Rock-Eval analyses; Petr Storch (Institute of Geology,
Prague, Czech Republic) kindly provided unpublished graptolite data
and his help is gratefully acknowledged. Florentin Paris (CNRS Rennes,
France) and an anonymous reviewer provided critical comments
useful for the improving of the paper.
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Contents lists available at ScienceDirect

Palaeogeography, Palaeoclimatology, Palaeoecology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p a l a e o

Organic-carbon deposition and coastal upwelling at mid-latitude during the Upper

Ordovician (Late Katian): A case study from the Welsh Basin, UK
T.J. Challands a,⁎, H.A. Armstrong a, D.P. Maloney a, J.R. Davies b, D. Wilson b, A.W. Owen c
a
Department of Earth Sciences, Durham University, Science Laboratories, South Road, Durham, DH1 3LE, UK
b
British Geological Survey, Kingsley Dunham Centre, Keyworth, Nottingham, NG12 5GG UK
c
Department of Geographical Earth Sciences, University of Glasgow, Gregory Building, Lilybank Gardens, Glasgow, G12 8QQ, UK

a r t i c l e i n f o a b s t r a c t

Article history: A lack of stratigraphical, sedimentological and geochemical data for sediment accumulation rates and
Received 2 October 2007 indicators of productivity and anoxia means that causative models for ancient black shales are largely
Received in revised form 19 July 2008 inferred from modern settings. Coastal upwelling has been suggested as a general hypothesis for Ordovician
Accepted 9 October 2008
black shale deposition within the Iapetus Ocean, but has not been directly tested. Despite anchizone
metamorphism we utilize a suite of geological and geochemical environmental proxy data (TOC wt.%, δ13Corg,
Keywords:
Ashgill
Ba/Al, P) to elucidate the mechanism for the origin of a single grey-black shale cycle within the upper Katian
Upper Ordovician succession of the Welsh Basin. Here we interpret organic carbon (OC)-rich deposition to be suggestive of a
Katian period of high photic productivity (higher TOC wt.%), with 12C and Ba enrichment, comparable to high
Organic carbon productivity events in modern coastal upwelling systems. Productivity proxy values are consistent with those
δ13Corg from margins where sedimentation rates are high (e.g. Gulf of California). Inter-bedded grey shales have low
Trace metal TOC wt.% more positive δ13Corg and marginally lower Ba and are interpreted as low productivity events.
Redox Thalassinoides, Planolites and Chondrites ichnofacies indicate changing seafloor oxygen levels. These show
Upwelling
predominantly dysoxic conditions even during the deposition of OC-poor grey shales. During an OC-rich
TOC
laminated hemipelagite event, oxygen levels declined at the sea floor before the deposition of the OC-rich
Climate
layers. Full anoxia was established early on in the deposition of OC-rich layers and the return to more oxic
conditions was rapid though fluctuating and coincident with the return of grey shale deposition. This pattern
suggests OC accumulation at the seafloor resulted from a complex interaction of productivity and
preservation. None of the widely used trace element redox proxies are reliable in anchizone metamorphic
rocks. Climate sensitive detrital proxies (K/Al and Ti/Al) indicate arid–temperate conditions in the basin
hinterland during the deposition of the OC-rich layers. The Welsh Basin was situated on the southern margin
of the Iapetus Ocean in (30°S) beneath the prevailing SE trade winds. We interpret the occurrence of OC-rich
laminated hemipelagite events to represent the intensification of upwelling, prior to the Hirnantian
glaciation, possibly having resulted from a strengthening of the trade winds, associated with stepped changes
in ice volume, and a more arid local climate.
© 2008 Published by Elsevier B.V.

1. Introduction climatic conditions it is necessary to determine whether the processes

Black shales provide important records of climate and atmo-
sphere–ocean interactions. The Early Palaeozoic oceans differed from
the Mesozoic and younger oceans because they experienced a mild
greenhouse climate (Yapp and Poths, 1992; Berner, 1994; Berner and
Kothavala, 2001) and were prone to permanent anoxia (Leggett, 1980).
However, black shales deposited in the Early Palaeozoic potentially
provide a detailed record of climate processes provided the mechan-
isms for their formation can be constrained. Under such different
⁎ Corresponding author. Current address: Total E & P UK Limited, Crawpeel Road,
Altens Industrial Estate, Aberdeen, AB12 3FG, UK.
E-mail address: tom.challands@total.com (T.J. Challands).
that formed Mesozoic to modern ocean black shales are also
applicable to Palaeozoic black shales. Processes for black shale
formation can typically be considered to be the product of increased
productivity or enhanced preservation (see Tyson, 1995, for a review).
Increasing productivity has been explained by: 1) increasing con-
tinental runoff (the Runoff model e.g. Beckmann et al., 2005; Bjerrum
et al., 2006), dominant at tropical latitudes, whereby increased
continental runoff introduces nutrients, increases productivity and
organic carbon (OC) export. Weathering regime proxies (K/Al, Ti/Al)
have recently demonstrated that fresh-water and detrital input into
basins is important for the formation of oxygen minima and the burial
of carbon e.g. the Cretaceous Ivorian Basin (Beckmann et al., 2005;
Bjerrum et al., 2006; Sobarzo et al., 2007). Along the upwelling margin
of Chile, high freshwater input suppresses upwelling through the

0031-0182/$ – see front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.palaeo.2008.10.004
396 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410

formation of a salinity stratified layer during wetter periods resulting
in lower oxygen values at depth (Sobarzo et al., 2007). 2) increased
oceanic/coastal upwelling (the Upwelling model e.g. Parrish, 1982;
Hay and Brock, 1992; Pope and Steffen, 2003) dominant at mid- to
high-latitudes in trade wind zones. Mechanisms for increasing
preservation include: 1) the Transgressive model, whereby transgres-
sion introduces additional nutrients and expansion of the deep ocean
oxygen minimum zone (OMZ) during sealevel rise promotes OC
preservation in high productivity shelf environments (Leggett, 1980),
2) restricted circulation, either global thermohaline circulation or
regional circulation such as in a restricted basin, and, 3) increased
burial efficiency of OC during increased sedimentation rate (Canfield,
1989).
The Transgressive model with unrestricted oceans may explain
thick black shales in Lower Palaeozoic basins (Leggett, 1980; Page
et al., 2007) but does not explain variation in productivity within black
shale successions, and in fact assumes it to be effectively constant
(Berry and Wilde, 1978, p. 271; Leggett, 1980, p. 150). For example, the
upper Katian (Rawtheyan Hirnantian British Stages) succession of
Dob's Linn, Scotland, located on the northern margin of the Iapetus
Ocean contains thin (b30 cm thick) black shale units alternating with
grey shale. These have been inferred to have been deposited at a time
of increased productivity (Armstrong and Coe, 1997) and global
eustatic, glacially-induced regression when the Iapetus Ocean was
much narrower and likely more restricted than has been previously
considered (Armstrong and Owen, 2002). Two oceanic events have
been recognized in the Dob's Linn succession (Fig. 1). The first, in the
mid Katian (Streffordian–Pusgillian boundary), is the sudden change
from anoxic to oxic conditions and the replacement of black with grey
shales. This has been interpreted as the onset of glacially-induced

Fig. 1. Stratigraphic chart (a) showing possible correlation between the sections at Dob's Linn (international boundary stratotype for the base of the Silurian System), lithostratigraphy
and graptolite biostratigraphy for Dob's Linn after Melchin et al. (2003); Underwood et al. (1997); Armstrong and Coe (1997). (b) Palaeogeographic map of Wales, England and
southern Scotland during the Late Ordovician showing inferred palaeobathymetry (based on Woodcock and Strachan, 2000). (c) Palaeogeographic reconstruction of Avalonia in the
Upper Ordovician showing position of the Welsh Basin (based on Cocks et al., 1997). (d) Palaeogeographic map of the Iapetus Ocean during the Late Ordovician (based on Herrmann
et al., 2005). This shows the distribution of the major continental land masses (L = Laurentia, S = Siberia, B = Baltica, A = Avalonia, DL = Dob's Linn, WB = Welsh Basin) and major surface
currents (solid arrows).
 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410 397

thermohaline circulation (Armstrong and Coe, 1997). The second is the
re-appearance of discrete black shale units within predominantly grey
shales during the upper Katian (anceps graptolite Biozone), and
was considered indicative of climatically-forced, Monterey-type
processes reflecting upwelling (Armstrong and Coe, 1997). The
presence of similar lithostratigraphic events in the Welsh Basin are
potentially contemporaneous with those at Dob's Linn and may
demonstrate that they could have been Iapetus Oceanwide reflecting
fundamental changes in the climate–ocean system before the onset of
glaciation.
Oceanic upwelling has been inferred from lower Katian (mid-
Caradoc) radiolarian cherts along the Iapetus Ocean margin from
Laurentia (Pope and Steffen, 2003) and in Wales from the presence of
phosphorites and radiolarites (e.g. Cave, 1965). The latter were
compared to phosphorites forming today at shelf-slope depths off
the California coast and attributed to climatic factors reflecting an
absence of currents and strong offshore winds or basin restriction
from the presence of a bathymetric barrier (Cave, 1965).
In this case study we use a suite of proxy data to test an upwelling
mechanism for an upper Katian black shale unit within the Welsh
Basin. Despite anchizone facies metamorphism, it has been possible to
reconstruct plausible palaeo-environmental conditions during
deposition from proxy data. Coastal upwelling is the preferred cause
of organic carbon (OC) enrichment of the sediments, and could have
been driven by changes in the strength of the prevailing trade winds.
Given the limitations of the extent and fidelity of the data, other
possible mechanisms are: 1) increased anoxia and, 2) marine
transgression. The upwelling hypothesis, however, is consistent with
known patterns of Late Ordovician climate change associated with the
developing Hirnantian glaciation.
2. Regional geology of the Ordovician of the Welsh Basin
Two major changes in oceanography can be identified in the Welsh
Basin during: 1) the mid-Katian (late Caradoc to early Ashgill) in the
linearis complanatus graptolite biozones (spinifera chitinozoan Bio-
zone) and, 2) in the late Katian anceps graptolite Biozone (umbilicata–
gamachiana chitinozoan biozones). At the first event, anoxic condi-
tions were terminated and the succession changes to predominantly
burrow-mottled lithofacies. These burrow-mottled grey shale units
have been mapped regionally as the Nantmel Mudstones Formation
(Davies et al., 2003; Fig. 2). During the late Katian a return to black
shale deposition is recognized (the “Red Vein”) comprising distinctive
alternating black laminated and grey burrow mottled siltstone and

Fig. 2. Regional Geology of the late-Katian of the Cardigan–Llangranog region, southwest Wales, UK. Abbreviations on regional location map BW = Builth Wells, CI = Cadair Idris,
LL = Llangranog, NE = Newcastle Emlyn, Rhay = Rhayader. Chronostratigraphy from Fortey et al. (2000) and Webby et al. (2004), chitinozoan biozonation from Vandenbroucke and
Vanmeirhaeghe (2007), graptolite biozonation and Time slices from Webby et al. (2004), lithostratigraphy from Davies et al. (2003).
398 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410

mudstones. The cause of this later change in lithofacies is unknown places and sections that allow safe access to the LH units and
and is the focus of this paper. interbedded OC-poor lithofacies have been selected: LH0 is accessible
The Red Vein (Fig. 2) crops out from the Cadair Idris region in the at Aberporth (SN 625 515), the base of LH1 is exposed at Tresaith (SN
north, south to Rhayader and Builth Wells regions and further west 280 516) and the upper boundary of LH1 crops out and is easily
around Newcastle Emlyn and north of Cardigan (British Geological reached at Traeth Penbryn (SN 289 522) (see Fig. 2). The same sections
Survey Llangranog 1:50 000 scale Sheet number 194; 2003). This for trace fossil analysis and geochemical analysis could not be used for
distinctive unit was first recognized in the Cadair Idris area by Pugh reasons of access. All trace fossil data were collected from LH0 at
(1923) and named on account of oxidation of the abundant iron Aberporth (SN 625 515, Locality 1), two sections spanning the lower
sulphide it contains. Three separate OC-rich laminated units have and upper parts of LH0 are conflated to a single composite section
previously been recognized in the Rhayader, Builth Wells and (Fig. 5). This 6.4 m-thick section was sub-sampled over six 40 cm
Llangranog regions (Davies et al., 1997; Schofield et al., 2004; Davies intervals, each separated by approximately 1 m.
et al., 2006) and interpreted as laminated hemipelagites (LH, Davies Geochemical samples were collected from two 5 m thick sections
et al., 1997). They consist of thin alternating laminae of dark grey, OC- spanning both the upper and lower boundaries of LH1. The lower
rich and medium grey OC-poor mudstone. boundary was collected at Tresaith (SN 280 516) and the upper
The LH units in the Llangranog region range in thickness from boundary at Traeth Penbryn (SN 289 522, Localities 2 and 3 respectively,
between 1036 m. Laminated OC-rich layers after 1.4 m above the base of see Fig. 2). Samples for trace element analysis were taken through LH1
LH0 contain abundant pyrite framboids and small nodules up to 1 mm in from organic-rich horizons at 20 cm intervals. There is no evidence at
length alongside finely-disseminated pyrite. The OC-rich laminated the sampling sites of secondary mineralization and all samples were
horizons are composed of a fine clay matrix and angular quartz grains up prepared from specimens with no surface alteration or fracturing.
to 0.25 mm and fine, platy muscovite and chlorite grains up to 0.175 mm Powders were then drilled from samples using a tungsten carbide drill
long. The medium grey OC-poor mudstone component of the LH units bit to homogenize and reduce matrix effects. Matrix effects were
occasionally contains thin fining-up sequences from silt to mudstone considered negligible due to the fine-grained nature of the samples.
and occasional very thin (b2 mm) fine-grained sand and are interpreted Sub-samples were taken for trace element and stable isotopic analysis.
as hemiturbidites (Stow and Wetzl, 1987) deposited in a slope-apron Sample digestion was carried out using HF-HN03 standard acid
system (Schofield et al., 2004). Within the LH, the absence of significant digestion techniques for ICPMS following the procedure of Ottley
grain-size variations between the OC-poor grey mudstones and OC-rich et al. (2003). A Perkin Elmer-Sciex Elan 6000 ICP-MS used in
units suggest the increase in OC content of the sediment was conjunction with a Cetac Direct Injection Nebuliser and a Cetac Aridius
independent of factors affecting sediment supply though precise Desolvating Nebuliser was used for analysis of trace elements. The
measures of sedimentation rate in ancient basin settings are difficult machine was calibrated using international rock standards W2, BHV01,
to measure (Wignall, 1994). AGV1, Be-N, NBS688 and BIR-1 and shale standards ScO-1, MAG-1 and
On regional maps of these areas the laminated hemipelagite units SGR-1 were also used for initial comparison of sample shale values. All
are termed lh'–lh″′ (British Geological Survey Rhayader 1:50 000 scale samples were analysed over three separate runs and reproducibility
Sheet numbers 178 and 179; 1997, British Geological Survey Builth throughout runs was monitored using SGR-1 (see Table 1). Relative
Wells 1:50 000 scale Sheet number 196; 2004, British Geological standard deviation (σ / mean× 100) was less than 11% in all runs.
Survey Llangranog 1:50 000 scale Sheet number 194; 2006). Herein, lh Internal precision for individual analyses was greater than 95%.
are capitalized and referred to numerically (e.g. LH1) to avoid confusion Normalisation to Al is a standard procedure for comparing element
between the letter ‘l’ and the number ‘1’ and to prevent inconsistency proportions, particularly where organic matter content is variable (e.g.,
in labelling. In the Llangranog region, an older LH horizon has been Tribovillard et al., 2005). Certain elements e.g. Ni are traditionally
recognized in this study and, following the British Geological Survey plotted against other detrital indicators e.g. Co. Spot samples for δ13Corg
numbering convention for these units, has been named LH0. and TOC wt.% were also collected from eleven other localities
The LH units are interbedded with grey burrow-mottled fine- representative of OC-poor facies below, between and above LH units
grained sandstones, siltstones and mudstones up to 25 m thick that and from LH0, LH2 and LH3 (Table 2, Fig. 4). All δ13Corg and TOC %
have been interpreted as fine grained distal turbidites resulting from measurements were made on a Thermo Finnigan MAT 253 Stable
periodic influx of coarser material (Davies et al., 2003; Schofield et al., Isotope Mass spectrometer at Durham University, Department of Earth
2004). They are hereafter referred to the OC-poor lithofacies. Sciences. TOC wt.% analysis of samples from 779.5–794.5 cm from the
Phosphatic nodules up to 1 m in length and phosphate horizons up to base of LH1 were conducted at Newcastle University Department of Civil
10 cm thick are present in both the organic-rich and organic-poor facies. Engineering and Geosciences using Rock Eval (6) Pyrolysis. Urea2, CH-7
Diffuse fine-grained phosphatic layers up to 10 mm thick are more and CH-6 standards were used for machine calibration and standard
frequent in the LH units and less common in the OC-poor lithofacies. In
the OC-poor lithofacies they occur in the light-grey silty mud layers.
Table 1
The thermal history of the Ordovician of the Welsh Basin has been
Reproducibility and error data for all shale ICP-MS runs using shale standard SGR-1
elucidated from illite crystallinity (Fettes et al., 1985; Robinson and
Bevins,1986; Bevins and Robinson,1988; Roberts et al.,1996). These data Run-1, n = 2 Run-2, n = 7 Run-3, n = 2
indicate a regional record of diagenetic to epizone facies metamorphism. Mean StDev RSD% Mean StDev RSD% Mean StDev RSD%
The Nantmel Mudstones Formation adjacent to the study area (British Al 6.1 0.15 2.47 6.92 0.5 7.2 18.66 1.37 7.36
Geological Survey 1:50 000 Sheet 193, Cardigan and Dinas Island) is of K 1.57 0.03 1.71 1.63 0.07 4.48 2.24 0.0 0.22
Ti 0.24 0.01 3.85 0.24 0.01 2.60 0.26 0.02 7.18
low anchizone grade. Darriwillian lower Katian aged shales immediately
V 120.56 3.88 3.22 121.82 2.70 2.22 124.12 7.81 6.29
south of Cardigan, have experienced late diagenetic to epizone Cr 29.62 0.34 1.16 33.31 0.95 2.85 33.60 1.87 5.56
temperatures (200–300 °C Lev et al., 2008) indicating burial to c. 4– Mn 0.03 0.00 0.00 0.03 0.00 2.43 0.03 0.00 4.29
6 km using a regional geothermal gradient of c. 50 °C/km (Bevins and Co 11.35 0.29 2.52 11.87 0.19 1.63 12.39 0.39 3.12
Ni 25.69 0.52 2.01 31.10 0.70 2.25 31.62 1.23 3.90
Merriman, 1988; Bottrell et al., 1990; Roberts et al., 1991).
Cu 60.60 0.44 0.72 60.73 0.53 0.87 63.84 1.91 3.00
Ba 299.63 1.89 0.63 295.20 8.16 2.77 263.07 8.72 3.32
3. Materials and methods Th 4.65 0.14 3.04 4.61 0.12 2.50 4.38 0.24 5.56
U 5.17 0.03 0.67 5.09 0.11 2.14 4.68 0.28 6.05
The best sections through the Red Vein are exposed in cliff sections Each run included both OC-rich and OC-poor samples. Al, K, Ti and Mn in wt.% oxide, all
along the coast of Cardigan Bay (Fig. 2). Accessibility is difficult in other elements in ppm.
 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410 399

Table 2 elements (Cu, Cr, Ni, V, Cd, Mo and U Tribovillard et al., 2005). These
δl3Corg and TOC for Cardigan coast line, Ceredigion, Wales elements form sulphides and complex with organic matter under
Sample Locality δ13Corg ‰ TOC % reducing conditions. OC-rich sediments are therefore typically
no. enriched in these metals (De La Rocha, 2004; Tribovillard et al.,
1 Gwbert Hotel (SN 161 500) – 29.46 0.29 2005, and references therein).
2 Carreg Lydan (SN 162 513) – 28.1 0.28 However some of these elements show significant mobility during
3 Mwnt (SN 192 519) – 30.95 0.27
late diagenesis to low grade metamorphic conditions. For example, at
4 Pen-y-Craig (SN 218 523) – 28.97 0.08
5 Aberporth (SN 258 515) – 30.70 0.15 these grades V becomes mobile and complexes with illite (Peacor et al.,
6 LH0 lower boundary, subsection 3 (SN 625 515) – 30.91 0.17 2000) rendering the frequently used redox proxies V/(V + Ni) and V/Cr
7 LH0 2 m, subsection 3 (SN 625 515) – 31.83 0.28 as unreliable. Uranium is also mobilized and enriched, whilst Th is
8 LH0 upper boundary, subsection 6 (SN 625 515) – 30.98 0.16 depleted during the formation of illite at low metamorphic grades
9 LH1 −80 cm from base of LH1, Tresaith (SN 280 516) – 30.5 0.14
10 LH1 −40 cm from base of LH1, Tresaith (SN 280 516) – 31.16 0.53
(Hannigan and Basu, 1998). Nickel, however, has been regarded as a
11 LH1 280 cm from base of LH1, Tresaith (SN 280 516) – 31.47 0.38 reliable redox proxy in organic-rich shales (Jones and Manning, 1994)
12 LH1 320 cm from base of LH1, Tresaith (SN 280 516) – 31.71 0.36 and has not been demonstrated to be mobile during low metamorph-
13 LH1 360 cm from base of LH1, Tresaith (SN 280 516) – 31.51 0.51 ism. We therefore use Ni/Co (Dypvik, 1984) and Ni/Al (Tribovillard
14 LH1 400 cm from base of LH1, Tresaith (SN 280 516) – 31.78 0.45
et al., 2005) ratios as an indicator of redox conditions in this study.
15 LH1 440 cm from base of LH1, Tresaith (SN 280 516) – 31.42 0.34
16 LH1 480 cm from base of LH1, Tresaith (SN 280 516) – 31.77 0.45
17 LH1 520 cm from base of LH1, Tresaith (SN 280 516) – 31.48 0.40 3.2. Productivity proxies
18 LH1 560 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.48 0.39
19 LH1 600 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.73 0.42 3.2.1. δ13Corg
20 LH1 640 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.53 0.45
The δ13Corg values of sedimentary organic matter are controlled by a
21 LH1 680 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.81 0.44
22 LH1 720 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.69 0.47 number of factors including organic matter composition and cell growth
23 LH1 760 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.12 0.29 rates (for a review see Freeman, 2001; Maslin and Swann, 2005, and
24 LH1 800 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.77 0.51 references therein). In the open ocean, sedimentary organic matter is
25 LH1 822.9 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.61
derived from marine and terrestrial sources. In pre-Devonian time there
26 LH1 823.5 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.61
27 LH1 824 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.524 was no extensive terrestrial vegetation (Peters-Kottig et al., 2006) and
28 LH1 824.8 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.255 organic matter in Ordovician rocks can therefore be considered entirely
29 LH1 825.9 cm from base of LH1, Traeth Penbryn (SN 289 522) – 31.52 0.258 marine in origin. Cell growth rates cannot be constrained in ancient
30 LH1 826.4 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.522 samples. Bulk sediment δ13Corg values are therefore only considered
31 LH1 826.9 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.281
indicative of shifts in mean oceanic isotopic composition.
33 LH1 827.5 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.604
33 LH1 828 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.469 δ13Corg values have been shown to yield an unaltered environ-
34 LH1 830 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.322 mental signal in greenschist facies rocks at Dob's Linn (Underwood
35 LH1 830.5 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.226 et al., 1997) and are therefore considered primary oceanic values in
36 LH1 831.6 cm from base of LH1, Traeth Penbryn (SN 289 522) – 30.3 0.324
this study. Nineteen δ13Corg samples were taken through the LH1. One
37 LH1 832.5 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.267
38 LH1 833.3 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.255
whole rock sample from each of the remaining three laminated
39 LH1 833.8 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.313 hemipelagite units (LH0, LH2 and LH3) was taken for δ13Corg as well as
40 LH1 835.3 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.3 nine samples taken from OC-poor lithofacies below, between and
41 LH1 836.9 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.275 above the LH units (Table 2).
42 LH1 837.9 cm from base of LH1, Traeth Penbryn (SN 289 522) – 0.255
43 LH1 842.4 cm from base of LH1, Traeth Penbryn (SN 289 522) – 29.8 0.2
44 LH2 (SN 293 523) – 31.73 0.41 3.2.2. Total organic carbon (TOC wt.%)
45 LH3 lower boundary, org.-poor facies (SN 296 528) – 30.8 0.44 TOC wt.% is known to correlate with more direct measures of
46 LH3 lower boundary org.-rich facies (SN 296 528) – 31.87 0.40 photosynthetic primary productivity such as total chlorophyll-a or
47 Highest Nantmel Mudstones Formation (SN 296 530) – 30.50 0.24
total steryl chlorine esters (Nara et al., 2005) and organic mass
Samples are listed from stratigraphically lowest (oldest) to highest (youngest), see Fig. 4 accumulation rate (Tyson, 1995; Vilinski and Domack, 1998; Kuypers
for stratigraphical plot of this data. et al., 2002, 2004; Twichell and Diester-Haass, 2002; Meyers and
Arnaboldi, 2005) and may therefore be suitable as a proxy for
deviation was less than 0.15‰ for all standards. Carbon isotope ratios productivity when supported by other proxy data (e.g. Ba). The burial
were expressed in the standard delta (δ) notation in per mil (‰) against efficiency of carbon is controlled by oxygen level and burial rate (for
the internationally accepted standard notation, Vienna Peedee Belem- example, Wignall, 1994; Tyson, 2001) and is therefore only likely to be
nite (VPDB). Analytical reproducibility of replicate samples using this representative of productivity when these two factors can unambigu-
method was better than 0.4‰. ously be shown to be constant. Thirty-five TOC samples were
measured through the OC-poor LH1 OC-poor section at Tresaith-
3.1. Redox proxies Penbryn and, like δ13Corg, one whole rock sample from each of the
remaining three laminated hemipelagite units (LH0, LH2 and LH3) was
3.1.1. Trace fossils measured for TOC wt.% as well as nine samples taken from OC-poor
The application of analysis of trace fossil assemblages and the degree facies below, between and above the LH units (Table 2).
of bioturbation has proven a strong tool for determining fluctuations in
sediment and basin oxygenation e.g. Ekdale and Mason (1988), Savrda 3.2.3. Trace elements
and Bottjer (1994), Savrda (1995), Löwemark et al. (2004). Ichnogenera The strong correlation between Ba and organic matter in marine
presence–absence, burrow diameter and bioturbation index data were sediments has led Ba values to be used to infer past export production
collected in line with standard procedures (Savrda and Bottjer, 1994; (De La Rocha, 2004). Dysoxic conditions are characterized by relatively
Savrda, 1995; Löwemark et al., 2004) at centimetre-resolution. low Ba concentrations (b500 ppm), increased Cd and U (Prakash Babu
et al., 2002). Though frequently used as a palaeoproductivity indicator,
3.1.2. Trace elements Ba has been found to be associated with sapropels formed in euxinic
The biological pump heavily influences the cycling, concentration basins (Brumsack, 2006). In these environments, Ba is highly mobile
and residence times of the redox-sensitive and sulphide forming trace and precipitates as barium-sulphides. Ba is thus an unreliable
 400
T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410
Fig. 3. Geochemical proxy data plotted against stratigraphical height above base of LHl, Traeth Penbryn. Error bars represent 1−σ.)
 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410 401

Fig. 4. Composite stratigraphical chart showing variations in δ13Corg and TOC % profile throughout the upper Katian (Cautleyan–Rawtheyan, Upper Ordovician) of the Cardigan–
Penbryn coastal section, Welsh Basin (SN 161 500 to SN 296–530). See Table 3 for details of precise sample locations.

indicator of productivity if euxinia can be demonstrated (Shimmield, metamorphic rocks we have normalized to Al which is also considered
1992; Prakash Babu et al., 2002). Ba is typically measured as a to be a detrital indicator (Tribovillard et al., 2005). We also plot raw
ratio against Th which is taken to represent terrigenous detrital Ba abundance (ppm) to test if an increase in Ba/Al is the product of
input (Shimmield, 1992). Due to the mobility of Th in low grade decreasing Al.

Table 4a
Table 3 f and t-test statistics for K/Al and Ti/Al through LH1, Traeth Penbryn
f and t-test statistics for Ba/Al and Ba (ppm) through LH1, Traeth Penbryn
OC-poor LH1 t-stat t-crit OC-poor LH1 f-stat f crit
OC-poor LH1 t-stat t-crit OC-poor LH1 f-stat f crit Mean Mean 2-tail Var. Var. 1-tail
Mean Mean 2-tail Var. Var. 1-tail K/Al 0.16 0.17 0.45 2.03 0.3 × 10− 3 1.92 × 10− 5 0.06 0.6
Ba/Al 2.7 × 10− 3 2.8 × 10− 3 0.6 2.02 1.69 × 10− 7 2.08 × 10− 8 8.12 1.74 Ti/Al 0.046 0.043 −3.77 2.03 2.1 × 10− 5 1.7 × 10− 6 0.08 0.57
Ba (ppm) 569.8 671.9 4.48 2.03 15878.6 866.6 18.32 1.75
Both the means and variances for K/Al are significantly different at α = 0.05 between OC-
Both the means and variances for Ba/Al and Ba (ppm) are significantly different at poor and OC-rich units. For Ti/Al, only the variance is significantly at α = 0.05 between
α = 0.05 between OC-poor and OC-rich units. OC-poor and OC-rich units is different.
402 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410

Table 4b 3.3. Climate sensitive detrital input proxies, K/Al and Ti/Al
Trace element data, LH1, Traeth Penbryn

Depth (cm) Al K Ti Co Ni Ba K and Al are mainly confined to the fine-grained aluminosilicate

1040 20.30 2.55 0.78 30.38 85.26 398.42 fraction, clay minerals and feldspars. Kaolinite which is rich in Al
1020 21.48 3.30 0.97 20.15 57.48 523.08 forms by intense chemical weathering under humid conditions
1000 22.57 3.54 1.00 21.41 61.18 558.80 whereas illites, which are rich in K, form under less humid
980 22.95 3.78 1.02 21.08 53.14 599.76
weathering conditions (Beckmann et al., 2005; Tribovillard et al.,
960 20.38 2.37 0.72 33.00 87.89 376.33
940 22.70 3.65 1.05 11.00 42.86 635.11 2005). Ti is concentrated in heavy minerals and is often transported
920 22.90 3.64 1.04 17.49 47.34 575.91 as part of the wind blown detritus, considered indicative of
900 20.94 3.18 0.86 18.60 51.35 566.61 weathering in arid environments. The K/Al ratios are therefore
880 22.98 3.74 1.05 28.99 55.59 500.10 used as a proxy of temperate to humid weathering and, similarly, Ti/Al
860 23.62 4.05 1.10 20.63 51.74 582.61
840 22.20 3.93 1.01 10.03 42.02 636.98
834.5 20.46 3.77 0.90 8.31 29.55 603.73
833.5 22.31 3.87 1.08 11.18 41.09 645.21
832 22.91 4.14 1.11 7.00 46.88 677.80
830.5 22.65 3.79 1.03 8.59 33.52 658.14
829.75 21.86 3.62 0.99 8.18 35.54 641.16
828.25 17.02 3.60 1.07 5.48 28.45 674.28
826.5 19.19 3.40 1.01 5.47 26.77 719.64
824 21.85 3.71 1.08 8.01 27.05 713.92
823 22.11 4.06 1.10 6.80 29.65 615.95
822 10.31 1.90 0.53 5.85 10.32 293.64
820.75 7.84 1.41 0.40 9.41 14.24 230.62
819.5 9.14 1.60 0.43 40.09 54.74 265.87
800 22.30 3.77 1.00 49.61 92.95 629.64
780 22.87 3.74 1.00 44.51 81.83 624.06
760 23.67 3.84 1.06 25.08 68.19 597.80
740 22.83 3.75 1.00 25.56 65.33 626.40
720 23.10 3.76 1.06 27.61 74.06 624.73
700 24.14 3.98 1.03 23.87 64.82 666.42
680 24.13 3.98 1.02 24.02 65.15 667.03
660 24.57 4.08 1.05 27.66 73.52 695.30
640 24.03 3.88 1.00 26.37 69.57 650.20
620 25.41 4.21 1.09 23.45 56.92 690.73
600 24.51 4.01 1.04 25.36 70.33 668.63
580 24.70 4.12 1.06 26.79 65.52 695.13
560 25.09 4.10 1.05 21.28 56.08 674.47
540 23.73 3.92 1.06 26.13 65.38 658.18
520 23.97 3.96 1.06 22.87 62.66 674.32
500 24.25 3.90 1.05 23.69 67.88 648.63
480 24.74 4.05 1.08 27.24 66.99 674.07
460 24.89 4.09 1.05 23.53 63.67 687.62
440 25.28 4.10 1.07 22.01 60.39 677.77
420 25.30 3.94 1.05 20.51 59.14 665.27
400 26.06 4.24 1.07 21.12 65.18 709.96
380 25.31 3.95 1.03 16.86 54.90 676.80
360 24.55 3.96 1.08 17.04 56.47 675.72
340 23.31 3.70 0.95 19.84 54.56 625.34
320 24.36 3.86 1.04 21.68 60.80 660.32
300 24.00 4.00 1.03 20.92 49.83 675.16
280 25.50 4.21 1.11 19.22 53.81 694.27
260 24.38 4.07 1.03 18.90 50.77 694.41
240 23.65 3.83 1.00 17.61 52.36 648.93
220 27.61 4.53 1.15 21.29 58.55 757.73
200 23.94 4.00 0.98 24.96 56.25 700.33
180 22.83 3.97 1.01 32.36 64.47 704.44
160 23.51 4.04 1.01 32.18 63.07 717.06
140 22.41 3.76 1.00 29.52 64.09 681.81
120 22.15 3.83 0.97 26.24 56.33 679.47
100 22.03 3.77 0.99 34.86 62.89 670.49
80 22.23 3.82 0.99 24.67 56.95 682.50
60 22.52 3.85 1.01 39.03 60.55 677.27
40 22.32 3.83 0.99 41.11 62.00 675.94
20 22.38 3.80 0.97 53.31 55.01 671.13
−40 22.63 3.28 0.99 21.23 60.44 572.60
−60 23.57 3.57 1.05 20.54 56.13 629.54
−80 22.67 3.64 0.98 17.79 48.51 640.86
−100 22.58 3.56 1.00 18.84 48.24 620.59
−120 23.38 3.81 1.10 18.65 45.47 663.89
−140 23.02 3.25 1.05 24.11 65.62 584.37
−160 22.64 3.64 1.06 18.56 45.67 649.10
−180 23.21 3.68 1.09 21.44 56.50 659.44
−200 20.26 2.98 0.90 22.06 53.96 520.37

Al, K, Ti are recorded as wt % oxide, Co, Ni and Ba are recorded as ppm.

All depths from the base of LH1.

Fig. 5. Cross-plots for a) TOC % vs δ13Corg, b) Ba vs. Al and c) Ba/Al vs. TOC %.
 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410 403

Fig. 6. Ichnofaunal responses to organic-rich sedimentation and development of anoxia at OC-rich unit LH0, Aberporth. See text in section 3.3 for details of sampling location.
404 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410
Fig. 7. Cross-plots for a) Co vs. Ni, b) Ni vs. Al and c) Ni/Al vs. TOC %.
may be regarded as a proxy for arid to humid weathering (Yarincik et al.,
2000).
4. Results
4.1. Productivity proxies: TOC wt.%,δ13Corg, Ba/Al
TOC values are higher during deposition of the organic-rich
laminated hemipelagite unit LHl. The maximum TOC value of
0.61 wt.% in LHl occurs 822.9 cm and 832.5 cm in the measured
section (mean value for LHl = 0.42 wt.%) whereas the minimum for OC-
poor oxic facies is 0.14 wt.% at 80 cm (mean value for measured
section = 0.31 wt.%, minimum for entire coast section = 0.08 wt.% at Pen
y Craig, SN 221 252, Fig. 4). Hydrocarbon source rocks typically have
N10 wt.% TOC (Tyson, 1995). A weak negative correlation occurs
between TOC wt.% and δ13Corg (r2 = 0.4), high TOC wt.% values
correspond to more negative δ13Corg values (Figs. 3 and 5a).
For LHl at Tresaith, the mean δ13Corg value is 31.6‰ (n = 14) and in
the OC-poor units, the δ13Corg mean is 30.7‰ (n = 5).
The more limited data from the other LH units suggest the LH
lithofacies is associated with a negative δ13Corg excursion of
approximately 1‰ (Fig. 4). δ13Corg values for each LH unit are between
30.5‰ (LHl) and 31.9‰ (LH3, mean for all LH units = 31.55‰) compared
to a mean value of 30.25‰ for all OC-poor samples.
δ13Corg values from the OC-poor lithofacies vary by up to 2.85‰
and exhibit an overall negative trend from the base of the measured
section at Gwbert Hotel (SN 160 509) from 28.10‰ to 30.50‰ at the
highest OC-poor lithofacies above LH3 (SN 296 530, Fig. 4, Table 2).
Ba/Al values in OC-rich facies vary between 2.5 × 10− 3 and 3.1 × 10− 3
and the mean is higher (mean = 2.8 × 10− 3) than the mean for OC-poor
facies (min. = 1.8 × 10− 3, max. = 4.0 × 10− 3, mean = 2.7 × 10− 3), see Table 4.
Values remain relatively constant through the lower 140 cm of LHl.
There is an abrupt decrease from 3.0 × 10− 3 to 2.7 × 10− 3 at 140 cm
(Fig. 3). Throughout the entire section, Ba/Al ratios and Ba values for
samples from OC-poor lithofacies are statistically lower than in the
OC-rich lithofacies (Table 3) and the correlation between Ba with Al is
good (r2 = 0.6; Fig. 5b). There is no apparent correlation between Ba/Al
and TOC (Fig. 5c).
4.2. Redox proxies
4.2.1. Trace fossils
Sub-sections 1 to 4 (Fig. 6) represent a transect through LH0 at
Aberporth (SN 625 515). Changing burrow diameter reflects changing
ichnogeneric content through the section. Thalassinoides is not
recorded in the LH0 section but is present with Planolites and Chon-
drites elsewhere in the OC-poor lithofacies where BI and maximum
burrow diameter are high (BI = 4, max. burrow diameter = ≥5 mm).
Thalassinoides, Planolites and Chondrites dominate the burrow
mottling of the sediment up to 2.8 m below the base of LH0. At 2.8 m
below the base of LH0 Thalassinoides disappears entirely and Planolites
and Chondrites only are present with BI ≤ 4 and maximum burrow
diameter ≤ 6 mm (sub-sections 1 to 3; Fig. 6). At 4.2 m above the base of
the section (0 cm in sub-section 4, Fig. 6) Chondrites is the only
ichnotaxon present and BI and burrow diameter are correspondingly
low (BI = ≤2, max. burrow diameter ≤ 2 mm). Between 20 and 38 cm in
sub-section 4 and between 22 cm and 38 cm in sub-section 5 strata are
devoid of trace fossils. Also, between the top of sub-section 4 and the
bottom of sub-section 5, no burrowing infauna are recorded. At the top
of sub-section 5 (1.42 m below the top of LH0 Aberporth section 2;
Fig. 6) Planolites is found again corresponding with an increase in
burrow diameters and BI (BI = ≤4, max. burrow diameter = 3 mm).
4.2.2. Geochemical redox proxies; Ni/Co
Ni values in LHl vary from 10.32 to 92.95 ppm and are typical for
those reported from Phanerozoic shales deposited beneath upwelling
systems (average shale = 68 ppm Brunsack, 1989; McCann, 1990;
Temple and Cave, 1992; Warnnig and Brumsack, 2000; Boening et al.,
2004; Borchers et al., 2005; Brumsack, 2006, see Table 5), see Table 4.
Values for samples at 780 cm and 780.75 cm above the base of the LHl
section at Penbryn are anomalously low (10.32 and 14.24 respec-
tively). Ni/Co values fall between 1.03 and 6.69 (mean=2.77), the
mean value for OC-rich LH1 is 2.49 (1.03 to 3.31) whilst values in the
OC-poor facies have a mean of 3.12 (1.37 to 6.69). Crossing the base of
the LHl, Ni/Co values fall abruptly to 1.03 (Fig. 3). Through LHl values
rise towards the centre (up to 3.31) and then decline towards the
upper boundary. At 2.5 cm below the top of the LHl, Ni/Co values fall to
1.4. In the base of the overlying OC-poor lithofacies this value rises
abruptly to 6.7.
Ni/Al values show a different pattern to Ni/Co. Values vary between
0.1×10–3 and 6.0×10–4 (mean=2.5 × 10− 4) throughout the same section
(Fig. 3) whereas in the OC-poor facies values vary from 0.1 × 10− 3 and
6.0 × 10− 4 (mean=2.3 × 10 − 4). In the OC-rich facies values range from
 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410 405

Fig. 8. Infaunal biofacies model of (Arthur and Sageman, 1994). Level 1 reflects anaerobic conditions both above and below the SWI, with laminated sediments, the highest levels of
preserved TOC and no evidence of benthic metazoans. At level 2 micro-burrowing disturbs the sedimentary laminae. Level 3 includes small deposit feeding pioneer ichnotaxa such as
Chondrites or Planolites. Level 4 is characterized by an increase in the size and density of Planolites and Chondrites burrows, but no additional ichnotaxa. At level 5 more complex
feeding traces such as Zoophycos and Teichichnus are found. Level 6 is indicated by the appearance of sediment-dwelling ichnotaxa (“domichnia”) such as Thalassinoides. Above level
6 all groups included produce high-diversity assemblages. The Chondrites, Planolites and Thalassinoides ichnocoenoses present in the OC-poor sediments and the transition to OC-rich
sediments represent infaunal biofacies levels 3–4. Interpreted oxygen levels at base of diagram (also from Arthur and Sageman, 1994) correspond to biofacies as shown.

2.1 × 10− 4 and 4.2 × 10− 4 (mean=2.6 × 10− 4). At the base of LH1, Ni/Al
values decrease slightly by 0.21 × 10− 4 (2.67 × 10− 4 to 2.46 × 10− 4). Values
gradually rise to a maximum of 5.9 × 10− 4 at the OC-rich OC-poor
boundary at 779.5 cm after which they decrease. In the OC-poor facies,
values rise again fluctuating between 4.3 × 10− 4 (960 cm) and 1.0× 10− 4
(822 cm). Ni shows a good positive correlation with Co (r2 = 0.6; Fig. 7a),
however, Ni is only weakly correlated with Al (r2 = 0.2; Fig. 7b) and TOC
wt.% (r2 = 0.2; Fig. 7c).
4.3. Weathering regime proxies, K/Al. Ti/Al
During organic-rich sedimentation there is a slight increase in K/Al
values by 0.018 (max. = 0.174, min. = 0.156, OC-rich LH mean = 0.165, OC-
poor lithofacies mean = 0.163) whereas Ti/Al values do not vary
significantly throughout the section (max. = 0.045, min. = 0.40, OC-
rich mean = 0.043, OC-poor lithofacies mean = 0.046). Peak values of
0.21 and 0.062 for K/Al and Ti/Al respectively are observed just within
the OC-poor lithofacies at 828.25 cm. Both the means and variances for
K/Al are not significantly different at a = 0.05 between OC-poor and OC-
rich lithofacies. For Ti/Al, only the mean is significantly different at
α = 0.05 between OC-poor and OC-rich lithofacies see (Table 4).
5. Preservation and productivity during deposition of OC-rich
laminated hemipelagite
5.1. Synchroneity of productivity, preservation and redox
The trace fossil associations throughout LH0 can be related to
published models for biofacies and ichnofacies responses in deterior-
ating oxygen environments (Rhoads and Morse, 1971; Sageman et al.,
1991) and can be used to investigate relative timing of anoxia and LH
deposition. Three distinct biofacies were recognized in the Rhoads
and Morse (1971) model; anaerobic, dysaerobic and aerobic, each
defined by a specific fauna and characteristic sedimentary fabrics.
Sageman et al. (1991) defined seven biofacies corresponding to dif-
ferent levels of oxygenation. Level 1 and 2 indicate anaerobic condi-
tions, level 2–6 dysaerobic conditions and level 7 aerobic conditions
(Fig. 8).
The presence and absence of the three dominant ichnotaxa through
LH0 allows the recognition of three distinct ichnocoenoses that
correspond to the biofacies levels described by Sageman et al. (1991):
1) Thalassinoides ichnocoenosis (biofacies level 6+), 2) Planolites
ichnocoenosis (biofacies level 4–5, and 3) Chondrites ichnocoenosis
(biofacies level 3). Oxygen depletion was initiated prior to the
appearance of macroscopic OC, indicated by the disappearance of Tha-
lassinoides, and declined gradually to fully anoxic conditions 1.4 m into
the event. In the upper part of LH0, O2 levels fluctuated between dysoxic
(Chondrites ichnocoenosis, biofacies level 3) and fully anoxic conditions.
O2 levels rise through into the overlying OC-poor shales reaching levels
close to the dysoxic–oxic boundary as marked by the reestablishment of
Thalassinoides. Ichnocoenosis boundaries do not coincide with the
boundaries of the LH suggesting OC burial flux/increased productivity
and redox were not synchronous.
During the deposition of LHl we observe, 1) higher TOC wt.% values
which correspond to more negative δ13Corg values when compared to
the OC-poor lithofacies, 2) an increase in the inorganic productivity
proxy Ba/Al and, 3) Ba values in OC-rich facies are higher than those
for OC-poor facies (except samples at 7.84, 9.14 and 10.31 cm), 4) Ba
values are variable (231 to 758 ppm) though are comparable to values
recorded in modern upwelling systems e.g. Peru margin and Baja,
California (see Table 5) but less than values from euxinic basins e.g.
Black Sea (1171 ppm Brumsack, 2006).

Table 5
Trace metal values for modern and Welsh Ordovician OC-rich black shales

Average Peru Namibia Gulf of Nod Glas, Modern Modern Tresaith, Tresaith, Black Sea Black Sea
shale2 margin1 mud lens2 California3 Caradoc, Wales4 turbidites2 abyssal clays2 Wales 16 Wales 26 unit 17 unit 27
Al 16.7 8.9 2.38 8.91 7.69 17.19 14.52 23.4 23.6 6.66 8.86
K 3.8 1.53 0.58 1.66 1.18 2.99 2.28 3.75 3.78 1.26 2.67
Ti 0.78 0.41 0.16 0.39 0.42 0.71 0.7 1.11 1.03 0.28 0.35
Ni 68 74 46 38 208 53.06 47.83 41 74 57 110
Ba 580 314 324 566 228 1427 558.9 558 658 604 1171

Al, K, Ti and Mn in wt.% oxide, all other elements in ppm. lBoening et al. (2004), 2Borchers et al. (2005), 3Brunsack (1989), 4Warnnig and Brumsack (2000), 5Temple and Cave (1992),
6
McCann (1990), 7Brumsack (2006).
406 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410
Table 6
End-member values for trace element ratios for depositional redox conditions, Ni/Co
(Jones and Manning, 1994)
Oxic Dysoxic Suboxic–Anoxic Euxinic
Ni/Co b 5.00 5.00 7.00 N 7.00
These patterns may suggest an increased productivity signal at the
appearance of LHl, however, because Ba values can be obscured by
either euxinic conditions (Brumsack, 2006) or diagenesis (Milodowski
and Zalasiewicz, 1991), it is possible our signal is obscured. Changes in
productivity at the transition from OC-poor lithofacies to OC-rich LH
are the most significant because this boundary represents a definite
change in OC-burial and/or productivity. The trace fossil redox data
from LH0 suggest that euxinic conditions were not achieved (in LH0 at
least) until after 1.8 m across the OC-poor lithofacies OC-rich
boundary. Ba can be considered reliable up until this point in terms
of diagenesis only if similar behaviour in redox is assumed for LHl. A
similar pattern in redox to LH0 may be applicable for LHl by inference
from Ba values which decrease approximately 2 m into the OC-rich
event when oxygenation is inferred to become euxinic and Ba
becomes mobile (Fig. 3). Where Ba values subsequently increase
dramatically at the OC-rich to OC-poor boundary, may possibly reflect
a ‘barite-front’ (Arndt et al., 2006; Brumsack, 2006), a zone of
precipitation of barium sulphate at a redox boundary following
mobilization of Ba under euxinic conditions.
Fig. 9. Light, middle and heavy Rare Earth Elements (La, Sm, Yb) plotted against stratigraphical height above base of LHl, Traeth Penbryn. Sample points are scaled to maximum error.
Bulk δ13Corg data suggest LHl contains more negative δ13Corg values
than the OC-poor units. We consider this pattern is not attributed to
changes in redox because sedimentary data and experimental data
studies demonstrate greater depletion of 13Corg in aerobic environments
(Lehmann et al., 2002). The difference in carbon isotope depletion
between diagenesis in an aerobic and anaerobic environment is only
0.16‰ (−1.81‰ and −1.65‰ respectively, Lehmann et al., 2002). The
selective loss of different compounds with different reactivities and 13C
values during the decay of organic matter can account for minor shifts
in the 13Corg of marine sediments (Freeman, 2001). However, for algal-
dominated organic matter, such as in the Ordovician oceans, this effect is
less than 1‰ (Freeman, 2001). Our values are greater than those
expected from a change in redox environment and from loss of different
compounds during diagenesis but consistent with increased burial of
12
C-enriched carbon. Also, the appearance of OC-rich LH is coincident
with a decrease in δ13Corg and not with the change in redox inferred in
LHl from the trace fossil distribution of LH0.
6. Stability of trace metal proxies
Both the values and patterns of Ni do not correspond to the sequence
of redox conditions shown by the trace fossils. Indeed, during the
deposition of LHl, Ni/Co values are indicative of fully oxic conditions and
during OC-poor they indicate dysoxia (Table 6). It is therefore clear that
Ni and Co concentrations have been altered during late diagenesis and/
or low-grade metamorphism and that the trace metals were mobile and
can no longer be used as a redox proxy in the studied rocks.
 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410 407

On the other hand, we are confident of the reliability of the Ba values
as a productivity proxy because of its enrichment in the OC-rich facies
relative to the Rare Earth elements (REE, La–Yb). The REE have elsewhere
been demonstrated to be mobile between turbidite beds and anoxic
hemipelagites (Milodowski and Zalasiewicz, 1991) but REE in the
measured transect of LHl are not enriched or depleted relative to OC-
poor facies (Fig. 9) indicating either no remobilization, remobilization
only on a small scale (e.g. cm–dm) or equal loss/gain of REE in each facies.
7. The origin of Welsh Basin the OC-rich laminate hemipelagites
The Runoff model predicts a decrease in products produced under
arid weathering conditions (K relative to Al) and an increase in fluvial
input indicated by higher Ti relative to Al and K. Though not of the
same magnitude as previous studies utilizing these proxies (e.g.
Beckmann et al., 2005), we record higher K/Al values and constant Ti/
Al values during deposition of LHl suggesting Avalonia experienced a
relative increase in arid weathering conditions at this time with less
fluvial input, making the means to produce a salinity-stratified basin
from increased continental freshwater runoff unlikely.
The slightly lower K/Al values found in OC-poor facies indicate a
relatively more humid climate with higher fluvial input but not
significant to develop salinity stratification. As the majority of the Late
Katian Welsh Basin deposits are represented by the OC-poor burrow-
mottled facies, we propose a more humid climate prevailed for much
of the late Katian prior to the deposition of the Red Vein.
Transgressive shales are formed during relative sea level rise, a
concomitant rise in nutrients/productivity and an upwards expansion
of the OMZ leading to increased preservation potential (Wignall,
1991). There are inconsistencies between the Transgressive model and
proxy data for the Welsh Basin LHl. The transgressive black shale
model of Page et al. (2007) is essentially a glacioeustatic variant of the
Runoff model, i.e. high nutrient input and productivity from glacial
meltwater with associated sealevel rise. The stability of our Ti/Al ratio
data throughout the OC-poor–LH–OC-poor transitions preclude
increased runoff, as previously mentioned. An alternative transgres-
sive black shale model, the ‘Expanding puddle model’ (Wignall, 1991)
involves expansion of the OMZ as sealevel rises. However, in the
productivity model, sealevel rise alone would only expand the OMZ
and raise the pycnocline if accompanied by increased productivity and

Fig. 10. Summary of all proxies during deposition of LH (a) Together, all proxies demonstrate that upwelling and oxygen deterioration commenced prior to the deposition of each LH
event. Falling oxygen conditions were relatively gradual until euxinia was established whilst oxygen recovery was rapid yet fluctuated and occurred prior to the cessation of LH
deposition. (b) Low productivity conditions were typified by weak upwelling and a depressed OMZ whereas high productivity conditions (c) occurred during high wind stress and
increased upwelling that recycled nutrients and 12C-enriched OC. ML = mixed layer.
408 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410

oxidation of organic matter which is not implied from sealevel rise.

Implicit in the Transgressive model is increased preservation of OC
(the Preservation model) from decreased thermohaline circulation
and ensuing stagnation of the oceans and/or basin. Such a scenario
could occur during global warming and melting of polar ice which
has not been demonstrated during deposition of the LH. However, the
approximately contemporaneous pre-Hirnantian Boda Event (Fortey
and Cocks, 2005) has been described as a global warming event
from faunal migrations but has in turn been refuted by (Cherns and
Wheeley, 2007) on the grounds of increased global distribution of
cool-water carbonates of Boda Event age.
The relative sea level curve for the Welsh basin (Woodcock, 1990)
is of too low a resolution to determine whether sea level was rising
during the anceps Biozone. An absence of grain-size changes during
the Red Vein suggests sealevel was invariant at the resolution of our
study.
In upwelling systems 12C-enriched CO2 derived from 13C-depleted
recycled organic matter is continually replaced from depth (Pancost
et al., 1999; Peeters et al., 2002), therefore the supply of 12C is
effectively limitless in an open system that has high OC preservation
such as an ocean with permanent deep water anoxia (Leggett, 1980).
Sequestration of this depleted carbon into the marine phyoplankton
through photosynthesis will result in sedimentary organic matter that
is similarly depleted (Pancost et al., 1999). Further to this, in modern
lacustrine (e.g. Hollander and McKenzie, 1991) and marine environ-
ments (e.g. Hofmann et al., 2000; Goericke, 1994; Goericke et al., 1994;
Freeman and Hayes, 1992), δ13Corg has been shown to decrease as the
concentration of dissolved CO2 [CO2aq] in surface waters increases and
as productivity increases. We therefore interpret δ13Corg in the current
setting in terms of a proxy for upwelling intensity as reported from
modern upwelling analogues (e.g. Pancost et al., 1999). Finally, as
recognized by Cave (1965), the presence of phosphate nodules
throughout the succession in both OC-rich LH and OC-poor sediments
could also be a further indication of nutrient-rich upwelling and the
stabilisation of the redox boundary (see also Ingall et al., 1993). Fig. 11. (a) Inferred trade wind positions and directions (from Parrish, 1982) over
Phosphorites have a limited occurrence at the present day, in Avalonia. Palaeogeography adapted from Hermann et al. (2004). (b) Detailed
palaeogeography of the northern margin of Avalonia in the British Isles (after Woodcock
particular being confined to zones of upwelling along west-facing and Strachan, 2000) and inferred position and direction of upwelling.
continental margins (e.g. the Peru margin and S. Africa Ingall et al.,
1993).
The LH unit analysed for inorganic and organic productivity At the present day the strength of the trade winds is related to the
proxies herein (LHl), in light of redox data from LH0, is thus interpreted intensity of the Hadley cell and is related to changes in equatorial high
to represent a period of higher productivity with increased organic pressure. During the Plio-Pleistocene, the position and intensity of the
carbon flux to the seafloor. The amount of marine organic carbon Hadley circulation (and associated trade winds) varied with changes
produced in the photic zone in the modern oceans is dependent in ice volume and solar insolation respectively (Rind, 1998; Ruddiman,
largely on nutrient availability in surface waters (Berger et al., 1989; 2000), the Hadley cell moving polewards during periods of glacial
Jahnke, 1990). We suggest coastal upwelling continually recycled bio- retreat and reduced latitudinal temperature gradient. The intensifica-
limiting nutrients (P, Ba) from depth and 12C-enriched CO2aq. The tion of coastal upwelling in the Welsh Basin and Iapetus Ocean from
elevated Ba levels and negative δ13Corg values observed in LHl are Hadley cell and trade wind position, prior to the Hirnantian glacial
consistent with being the product of increased productivity from maximum, may therefore reflect latitudinal movement of the Hadley
upwelling (Fig. 10a, c). During these periods of high productivity, cell during an increase (northward movement of the Hadley cell) or
increased oxidative respiration of organic matter resulted in; 1) the decrease (southward movement of the Hadley cell) in the size of the
seafloor becoming increasingly oxygen depleted and, 2) an upwards Upper Ordovician ice sheet, depending on where the Hadley cell was
expansion of the OMZ. Organic-poor shales were deposited during initially positioned relative to Avalonia. Subsequent short-term cyclic
periods of decreased productivity and organic carbon flux and a return patterns of increased upwelling (possibly represented by LH0–LH3)
to more oxygenated seafloor ensued (Fig. 10b). could reflect orbitally-moderated changes in solar insolation and ice
Coastal upwelling intensity can vary with a number of factors, volume.
but the most important of these is the strength of the offshore
winds (Hay and Brock, 1992). During the late Katian, global 8. Conclusions
atmospheric circulation models (Parrish, 1982) and palaeoconti-
nental configurations (Hermann et al., 2004) infer that the Welsh The fine grained siliciclastic rocks of the Welsh Basin record an
Basin could have been located beneath the zone of southwesterly evolving sequence of events during the transition from Ordovician
prevailing trade winds on a northwestwards facing coast (Fig. 11). greenhouse to icehouse climate states. We postulate that the proxy
We hypothesize that the cyclic nature of black shale deposition in records from one OC-rich laminated hemipelagite unit (LHl) presented
the Red Vein reflects the changing intensity of the upwelling system herein indicate short-lived, cyclic enhanced coastal upwelling and
in response to the changing strength of the offshore trade winds surface organic productivity along the southern Iapetus margin.
(see also Cave, 1965). Increased upwelling and productivity could have been induced by
 T.J. Challands et al. / Palaeogeography, Palaeoclimatology, Palaeoecology 273 (2009) 395–410
increased wind stress from the intensification of coast-parallel to
offshore SE trade winds. Higher productivity and OC supply to the
deep ocean would likely have resulted in a rise in the position of the
OMZ, which breached the semi-restricted Welsh Basin, in response to
increased oxygen depletion of the water column. We hypothesize that
black shale deposition may have been controlled by complex climate–
ocean–biosphere interactions possibly reflecting responses to ice
volume changes during the developing end-Ordovician glaciation.
Replication of these results from other OC-rich units of similar age in
the Welsh Basin (e.g. LH0, LH2 and LH3) is necessary to further support
this interpretation. Metamorphism to anchizone metamorphic facies
reduces the number of ocean–environment proxies that can be a used
to elucidate palaeoenvironmental conditions. We consider the
productivity proxies, Ba/Al, TOC %, δ13Corg and the climate-sensitive
detrital input proxies K/Al and Ti/Al to be robust and could be widely
applied in the slate grade rocks commonly found in orogenic belts.
Acknowledgments
T. J. Challands would like to acknowledge the receipt of a University
of Durham Postgraduate Scholarship and a British Geological Survey
British Universities Funding Initiative grant. Comments by P. B.
Wignall and J. A. Zalasiewicz have helped to greatly improve the
manuscript. J. R. Davies and D. Wilson publish with the permission of
the Executive Director, British Geological Survey (NERC).
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