Cretaceous Research (2001) 22, 243–257

doi:10.1006/cres.2001.0253, available online at http://www.idealibrary.com on

Geochemical signature and related

climatic-oceanographic processes for early
Albian black shales: Site 417D, North Atlantic
Ocean
Peter Hofmann, Werner Ricken, Lorenz Schwark and Detlev Leythaeuser
University of Cologne, Department of Geology, Zülpicher Str. 49a, 50674 Cologne, Germany

Revised manuscript accepted 24 January 2001

A sediment sequence which may contain the early Albian OAE 1b was investigated in a deep-water (3800 m) open-ocean
environment at Site 417D, western North Atlantic Ocean. Redox cycles, which contain black shale intervals and occur in the
early Albian M. gracilis radiolarian Biozone, were studied in order to show processes and climate-associated controlling
factors during the deposition of early Albian sediments. The black shale intervals are characterized by the enhanced
accumulation and preservation of marine-derived organic matter as determined by Rock-Eval pyrolysis and organic petrology.
The presence of laminated sediments, the relationships between organic carbon, iron and total sulfur, pyrite size analysis and
trace-metal enrichment indicate the periodic prevalence of anoxic conditions in the pore waters, which may at times have
extended to the sediment/water interface. Changes in the mineralogical composition throughout the black shale-dominated
interval, i.e., quartz content and clay-mineral assemblage, resulted in the variation of the major-element chemistry and
probably reflect cyclic climatic changes in northern Africa combined with flooding of coastal lowlands during an overall
transgressive phase in the early Albian. The geochemical signatures observed at different scales demonstrate a genetic link
between the climate system on land and processes in the deep ocean during the deposition of black shales in deep-water
environments of the western North Atlantic.  2001 Academic Press

K W: Oceanic Anoxic Event 1b; black shales; redox conditions; climate forcing; early Albian; North Atlantic.

1. Introduction demonstrate a relationship between OAE develop-

The recognition of isochronous, organic matter-rich
black shales (total organic carbon >1%) in pelagic
Cretaceous intervals on a global scale resulted in the
concept of ‘Oceanic Anoxic Events’ (OAEs) charac-
terized by enhanced burial of organic matter (e.g.,
Schlanger & Jenkyns, 1976; Arthur & Schlanger,
1979; Jenkyns, 1980). Initially two OAEs were intro-
duced for the Cretaceous: the Aptian/Albian OAE 1
and the Cenomanian/Touronian OAE 2. Subsequent
investigations led to the recognition of a third OAE in
the Coniacian/Santonian (Arthur & Schlanger, 1979;
Jenkyns, 1980) and to a further division of the exten-
sive time period covered by the OAE 1 into four
distinct sub-events of ocean-wide dysoxia/anoxia
separated by dominantly oxic oceanic conditions:
early Aptian OAE 1a, early Albian OAE 1b, and late
Albian OAE 1c and 1d (Arthur et al., 1990; Jenkyns,
1991; Bralower et al., 1993, 1994; Erbacher, 1994;
Erbacher et al., 1996, 1999; Erbacher & Thurow,
1997, 1998). Erbacher et al. (1996) were able to
ment and the resulting ‘black shale’ deposition,
radiolarian evolution patterns, and sea-level change.
They observed that OAEs occurred either during
transgressive periods at times of maximum flooding
and, hence, sea-level high stands (e.g., the OAEs 1a,
1b, 1d and OAE 2) or during regressive periods at
times of maximum sea-level fall (OAE 1c). OAEs
associated with transgressive periods are interpreted as
having been caused by the leaching of nutrients from
coastal lowlands, which led to increased fertilization
and a rise in productivity in the adjacent ocean basins
(e.g., Erbacher et al., 1996; Figure 1). As a result,
oxygen minimum zones expanded ocean-wide, and
high-productivity anoxia developed in the pelagic
depositional environment, which fostered the preser-
vation of marine organic matter (Type II). Erbacher
et al. (1996) coined the term p-OAE (p=productivity)
for this type of OAE and noted a correlation with
extinction of, and/or radiation events in radiolaria.
By contrast, OAEs that developed during regressive

0195–6671/01/020243+15 $35.00/0  2001 Academic Press

244 P. Hofmann et al.
Figure 1. Schematic model for the generation of
productivity-related Oceanic Anoxic Events (after
Erbacher et al., 1996).
periods were caused by a high input of detrital organic
matter (d-OAEs) and high sedimentation rates in
the pelagic realm, which resulted in the preservation
of black shales containing mainly type III organic
matter. D-OAEs are characterized by high radiolarian
diversities and radiation.
In contrast to other mid-Cretaceous OAEs (e.g.,
OAE 1a and OAE 2), there are few data on the early
Albian OAE 1b (Erbacher & Thurow 1998). This is
recorded in the Hedbergella planispira foraminiferal
Zone and the Prediscosphaera columnata nannofossil
Zone (Bralower et al., 1993). Dating based on calcar-
eous plankton creates problems if the effects of this
OAE are investigated in deep-water environments
because the carbonate compensation depth (CCD)
was shallow during most of the Albian (e.g., Bralower
et al. 1994). Deep-water environments were, however,
sensitive monitors for the intensity of an OAE and the
processes which controlled it. Fluxes of marine and
terrestrial organic matter that survived transit through
an extensive water column are recorded in the sedi-
ments that were deposited and, thus, can be used to
study the influence of climate-controlled processes on
the extent of the development of anoxia. The dating
problem has been solved for the North Atlantic with
the introduction of an improved mid-Cretaceous
radiolarian zonation (Erbacher & Thurow, 1997,
1998), which is calibrated to the established foramin-
iferal and nannoplankton zones and now allows the
investigation of the event in sub-CCD sites. OAE 1b
was assigned to the lowermost M. gracilis radiolarian
Zone by Erbacher & Thurow (1998).
Chemical investigations of the OAE 1b are pres-
ently limited to determinations of organic-carbon con-
tent (Bralower et al., 1993) and the documentation of
positive shifts in the
13Ccarbonate curves that are
associated with most major OAEs (Scholle & Arthur,
1980; Weissert, 1989; Weissert & Lini, 1991;
Erbacher et al., 1996, 1999; Erbacher & Thurow,
1997). We studied black shale deposits at Site 417D
with a set of geochemical tools in order to achieve a
better understanding of the complex processes that
led to the deposition of black shales in the North
Atlantic Ocean. Of particular interest was the inter-
action of climate-forced processes on land and sea-
level change, as well as their links to processes that
control ocean fertility.
The p-OAE model of Erbacher et al. (1996) implies
several geochemical consequences that can be investi-
gated in more detail (Figure 1). According to this
model, p-OAEs were triggered by the leaching of
nutrients from coastal lowlands during periods of
maximum flooding, thus causing fertilization of the
ocean and an increase in productivity, which in turn
resulted in a high flux of marine organic matter to the
sea floor. As a consequence, oxygen-minimum zones
expanded and high-productivity anoxia developed on
the sea floor even in the pelagic realm. High accumu-
lations of marine organic matter can be readily traced
by the determination of organic-carbon contents in
conjunction with pyrolysis techniques and kerogen
microscopy, both of which can be used to distinguish
the type of accumulated organic matter. The develop-
ment of anoxic bottom-water conditions in the sedi-
mentary record can be recognized based on C/S ratios
(Leventhal, 1983; Berner, 1984; Raiswell & Berner,
1985), Fe/TOC/S relationships (Dean & Arthur,
1989), framboidal pyrite size-distribution patterns
(Wilkin et al., 1996), and the enrichment of selected
redox-sensitive trace elements, as noted for other
OAEs (e.g., Brumsack, 1980, 1986; Arthur et al.,
1990; Rachold, 1994; Calvert & Pedersen, 1996).
2. Material and methods
Geological background for Site 417D
Site 417 is located to the south of Bermuda Rise
immediately north of Vema Gap (Shipboard Scientific
Party Leg 51, 1979). Erbacher et al. (1996) and
Erbacher & Thurow (1997) recognized the presence
of an organic matter-rich interval in core 19, which is
located in the lowermost M. gracilis radiolarian Zone
and displays a radiolarian extinction/radiation pattern
similar to those observed for the OAE 1b at other early
Albian sites (Figure 2). Erbacher & Thurow (1997)
could only tentatively identify this interval as contain-
ing OAE 1b. The exact identification of OAE 1b, is
however, still under discussion because of the lack of
calcareous fossils for cross-correlation and a poor
core-recovery record in the Aptian/Albian. Palaeo-
bathymetric estimates by Sikora & Olsson (1991)
yielded an Albian water depth of 3800 m for site
 Geochemical signature and related climatic-oceanographic processes

Figure 2. Stratigraphy, lithology and palaeogeographic reconstruction of Site 417D, Leg 51, southern Bermuda Rise, northwest Atlantic, with emphasis on OAE 1b
(compiled from Erbacher & Thurow, 1998 and Hay et al., 1999). P. pseudomacro., Pseudodictyomitra pseudomacrocephala; M. gracilis, Mita gracilis; H. crassum,
Halesium crassum; R. tic., Rotalipora ticinensis; R. ang., Rhagodiscus angustus; C. lit., Chiastozygus litterarius.
245
246 P. Hofmann et al.
417D, which is in good agreement with the presence
of carbonate-free sediments, indicating a deep-water
position below the CCD. Thus, Site 417D is, to our
knowledge, so far the deepest dated record which may
contain OAE 1b in the deeper parts of the Albian
North Atlantic.
Analytical methods
Core 19 was described in detail in order to document
the dominant cycle pattern as expressed by lithology,
degree of lamination and bioturbation patterns.
Samples for geochemical analysis were chosen to
cover all major lithologies. Total carbon and total
sulfur determinations were carried out with a LECO
CS-225 instrument on ground samples. Total organic
carbon (TOC) measurements were conducted with
the same instrument after treatment with hot hydro-
chloric acid. Rock Eval Pyrolysis was performed with
a Rock Eval plus instrument from Vinci Technologies
according to the method described by Espitalié et al.
(1985) on powdered whole rock samples with a TOC-
content of more than 0.3% following the suggestions
of Peters (1986). Maceral analysis was performed by
point counting, using ground sample powder embed-
ded in an epoxy resin, on polished surfaces with a
Zeiss Axioplan microscope under blue and white light
excitation. Pyrite size determinations were conducted
on the samples prepared for maceral analysis. Be-
tween 50 and 100 framboid diameters were deter-
mined per sample and subjected to statistical analysis.
Inorganic sediment chemistry was determined by
X-ray fluorescence analysis on powdered samples that
were heated for four hours at 105C. Fused discs were
prepared and analyzed using a sequential X-ray spec-
trometer (Phillips PW2400) calibrated with natural
and synthetic standards.
3. Results
Sedimentology
The investigated succession in core 19 consists of
alternating productivity/redox cycles of laminated
black shales and bioturbated pale to dark green clay-
stones. The thickness of the observed cycles increases
towards the centre of the black shale interval that may
contain OAE 1b and is characterized by a successive
increase in the organic-matter-rich parts of the cycles
(Figure 2). The gradual onset and termination of
‘black shale’ deposition is characterized by bedding
cycles that are dominated by bioturbated green clay
members. Lamination in the black shale part of the
bedding cycles becomes more pronounced towards
the center of the OAE, where the bioturbated intervals
of the productivity cycles decrease in thickness. The
pale green and dark green claystones of the bedding
cycle contain chondrites or fucoid-type burrows with
black infillings (Shipboard Scientific Party Leg 51,
1979). Black shale intervals are, however, only occa-
sionally bioturbated, but still display a fine parallel
lamination. The core interval can be subdivided into
23 bedding cycles based on sediment colour and
bioturbation/lamination patterns (Figure 2).
Bulk sediment chemistry
Based on XRD studies by Mann & Müller (1979) and
Brosse (1982), the mineralogical composition of the
sediments of core 19 consists mainly of quartz and
clay minerals. Feldspars, pyroxenes, barite and apatite
occasionally occur in traces as accessory minerals. The
clay fraction is composed of smectite, illite and mixed
layer minerals of the illite/smectite type (I/S-mixed
layer minerals). Semi-quantitative analysis of the clay
mineral composition of the <2 m fraction of four
samples from core 19 by Brosse (1982) yielded 30%
illite, 20–50% smectite and 20–50% I/S-mixed layer
minerals. Our microscopic studies revealed the
ubiquitous presence of pyrite in varying amounts (see
further discussion below), which was also noted by the
Shipboard Scientific Party Leg 51 (1979). The min-
eralogical studies are in good agreement with the
chemical data of this study. The silica content of
the sediments varies between 62.2 and 81.53% SiO2,
the aluminum content between 4.39 and 10.25%
Al2O3 and the organic carbon content between 0.03
and 7.12% TOC, suggesting a sediment composition
controlled primarily by a three-component system
consisting of silica, aluminosilicates and organic
matter (Figure 3). The analysis of the data set in the
three-component system SiO2-Al2O3-TOC shows
that the SiO2/Al2O3 ratios are too high to be explained
by compositional variation of the aluminosilicate
phase (illite, smectite and I/S-mixed-layer minerals)
alone, and, hence, indicates the ubiquitous presence
of an additional SiO2 phase. Erbacher (1994) re-
corded a low content of radiolarian tests in the interval
studied, which may have caused some of the observed
variation but is unlikely to have controlled the overall
trend. XRD data from Mann & Müller (1979),
Brosse (1982) and our own data do not indicate the
presence of opal C-T but do record quartz in high
abundance.
The potassium, magnesium, titanium, iron and, to
a lesser extent, sodium concentrations correlate with
the aluminum content (Table 1) and are, therefore,
 Geochemical signature and related climatic-oceanographic processes
Figure 3. Ternary diagram SiO2-Al2O3-TOC showing the
mixing relationships of the main sediment components
of core 19. White stars indicate the average composition
of smectite and illite; the shaded field shows the
naturally occurring compositional variation (based on
data from Weaver & Pollard, 1975 and Weaver, 1989).
related to compositional variations in the alumino-
silicate component. Calcium and phosphate are also
closely correlated, which conforms with a concen-
tration of these elements in apatite (Table 1).
Aluminum-normalized element ratios were used in
order to investigate down-core variation in the com-
position of the detrital fraction, thus eliminating dilu-
tion effects by other sediment components (e.g.,
organic matter and pyrite). The downhole logs of the
Si/Al ratios display wide variation between 5.7 and
16.6, and show a distinct drop, which coincides with
the black shale-dominated part of the core. The shift
in Si/Al ratios indicates an increase in the aluminosili-
cate component relative to the detrital quartz compo-
nent. The clay mineral assemblage is dominantly illite
and, to a minor extent, I/S mixed-layer minerals
(Weaver & Pollard, 1975; Weaver, 1989). Their
relative abundance can be traced by K/Al ratios.
The downhole logs for the K/Al and Si/Al ratios
show similar trends (Figure 4). K/Al ratios and Si/Al
ratios show a good correlation for the entire data set
(Figure 5) and, hence, suggest a common source for
the carrier phases of both elements (i.e., quartz and
illite).
The most significant shift in the bulk inorganic
chemistry of the sediments from core 19 occurs with
the onset of ‘black shale’ deposition in the interval
from 316.2 to 317.4 m; other element ratios show
only minor variation. This interval is characterized
by a drop in the relative abundance of quartz, as
indicated by the shift in Si/Al ratios. In the same
interval, the otherwise uniform clay-mineral assem-
blage changes towards a more smectite- or I/S mixed-
247
layer-rich assemblage at the expense of illite. Lever &
McCave (1983), among others, argued that in regions
away from the action of ice rafting, the terrigenous
fraction of pelagic sediments was mainly transported
to the sea-surface by wind. Dust in the deep sea,
therefore, provides a record of the climatic develop-
ment of the source region (Rea, 1993).
In a comprehensive study of the clay-mineral as-
semblage of the Albian North Atlantic region, Robert
& Chamley (1982) were able to demonstrate that the
clay-mineral composition was a function of the pri-
mary source input, not a product of later diagenesis.
These authors came to the conclusion that the illite
was detrital in origin and identified the African margin
as the main source of illite in the Albian North
Atlantic. Smectite is thought to indicate climate
conditions with a pronounced dry/humid contrast
(Robert & Chamley, 1982; Chamley, 1989). As dis-
cussed above, the good correlation of the Si/Al (proxy
for quartz content in clays) and K/Al ratios (proxy for
illite content) in core 19 suggests that quartz was also
mainly derived from source areas in northern Africa.
Lever & McCave (1983) argued, on the basis of the
distribution and composition of eolian components in
Cretaceous sediments, that eolian input into pelagic
realms was an important component in the North
Atlantic region starting at least in Early Cretaceous
times. Maximum eolian input occurred at latitudes
from 20–30N. Palaeogeographic reconstructions for
Site 417D indicate a palaeolatitude between 15 and
20N, hence, close to the belt of the assumed maxi-
mum eolian input (Philip et al., 1993). Numerical
simulations for mid-Cretaceous atmospheric circu-
lation by Barron et al. (1995) and Poulsen et al.
(1998) yielded surface wind patterns similar to
present-day winds, indicating dominant eolian input
from the African continent. These simulation results
are also supported by the palaeogeographic distri-
bution of palygorskite in Albian and Cenomanian
deposits of the North Atlantic, as reported by Pletsch
et al. (1996), which suggests airborne transport of this
mineral from the centres of formation in northern
Africa and southern Spain into central parts of the
North Atlantic region. The most probable source for
illite and quartz at site 417D appears, therefore, to be
a region between 20 and 30N in northern Africa. The
observed stratigraphic variation of these sedimentary
components may suggest temporal fluctuation of wind
intensities, which were probably climate-controlled,
and provide a record of the northern African climate.
Intervals dominated by quartz and illite may indicate
periods of intense physical erosion, while more
smectite-rich intervals represent climatic conditions
suitable for the neoformation of clay minerals, i.e.,
 248

Table 1. Inter-element correlation matrix.

Al2O3 CaO Co Cr Fe2O3 K2O MgO MnO Na2O Ni P2O5 Stot SiO2 Sr TiO2 TOC V

Al2O3 1.00000
CaO
0.15730 1.00000
Co 0.07885 0.00200 1.00000
Cr
0.40167 0.12886 0.28466 1.00000
Fe2O3 0.67260 0.12654 0.14374
0.20053 1.00000
K 2O 0.95057
0.16215 0.04591
0.44007 0.63189 1.00000
MgO 0.94929
0.03018 0.14659
0.37483 0.74374 0.87324 1.00000
MnO
0.05959 0.46324
0.11251
0.37764 0.19531 0.00660 0.10838 1.00000
Na2O 0.58376 0.24554 0.14487
0.01648 0.59491 0.55107 0.62739 0.03930 1.00000
Ni
0.03803 0.15279 0.72465 0.63254 0.22096
0.12913 0.03070
0.15201 0.16512 1.00000
P. Hofmann et al.

P2O5
0.03129 0.77602 0.01184 0.26761 0.26961
0.03645 0.07511 0.18898 0.45201 0.21801 1.00000
Stot 0.38244 0.30519 0.05346 0.08419 0.73407 0.32102 0.38568
0.03327 0.59147 0.29549 0.36596 1.00000
SiO2
0.43281
0.39785
0.14806
0.21505
0.65936
0.36731
0.50563
0.01256
0.72452
0.41171
0.60402
0.76038 1.00000
Sr 0.53675 0.37070 0.18647
0.24208 0.62300 0.48867 0.63912 0.17803 0.49587 0.12957 0.44891 0.44483
0.54477 1.00000
TiO2 0.88008
0.26704
0.09842
0.30279 0.40027 0.87227 0.75745
0.15946 0.52196
0.15619
0.10263 0.28394
0.34960 0.25316 1.00000
TOC
0.37095 0.29013 0.15622 0.75331
0.02610
0.42551
0.31053
0.17195 0.17955 0.61440 0.46820 0.36020
0.53596
0.12063
0.26084 1.00000
V 0.14923 0.03951 0.15257 0.38131 0.16202 0.13080 0.12063
0.18588 0.40524 0.40438 0.19056 0.34638
0.51109
0.10476 0.26078 0.53756 1.00000
 Geochemical signature and related climatic-oceanographic processes 249

Figure 4. Geochemical logs for Si/Al, K/Al, Na/Al, Mg/Al and Ti/Al ratios. Note the compositional variation in the interval
316.20–317.40 m, indicating fluctuation in quartz (Si/Al), illite (K/Al) and smectite (Na/Al) input. For discussion of the
processes that led to the variation, see text; for key to lithologies, see Figure 2. Black shale intervals are shaded.

with pronounced dry/humid contrast (Robert &
Chamley, 1982; Chamley, 1989).
OAE 1b took place during a period of assumed
sea-level rise (e.g., Erbacher et al., 1996; Price et al.,
1999), which may also have affected the composition
of detrital sediments. The flooding of coastal lowlands
during a sea-level rise would have decreased the
Figure 5. Correlation of Si/Al (proxy for quartz content)
and K/Al ratios (proxy for illite content) suggesting a
common detrital source for quartz and illite.
potential for erosion on the surrounding landmasses
of a basin, thus diminishing the amount of detritus
(e.g., quartz and illite) available for eolian transport to
more central parts of the basin (Haq, 1991).
Several authors have suggested a climate-controlled
origin of bedding rhythms containing interlayered
black shales for the Cretaceous and interpreted these
cycles as recording short-term climatic fluctuations of
the order of a few tens of thousands to 100 ky (e.g.,
Arthur, 1979; Arthur et al., 1984, 1990; Dean &
Arthur, 1986; Fischer, 1986, 1991; Bottjer et al.,
1986; Herbert et al., 1986; de Boer, 1991a; van
Buchem et al., 1995; Hofmann et al., 1999a) that were
related to the periodic modulation of the Earth’s
orbital parameters as described by Milankovitch
(1941). Even though sedimentation rates are only
poorly constrained for the Albian sediments of hole
417D, the influence of orbital fluctuations on the
composition of detrital sediment components can still
be tested. Ratios of spectral peaks revealed by time-
series analysis should correspond to those of the
frequencies predicted by Milankovitch. For this analy-
sis the mid-Cretaceous frequencies calculated by
Berger & Loutre (1994) were used, i.e., 18.5 and
22.3 ky for precession, 39 and 51 ky for obliquity, and
95, 123 and 413 ky for eccentricity. We analyzed the
250 P. Hofmann et al.

Si/Al and K/Al logs for the presence of orbital fre-

quencies with spectral techniques (Figure 6). Spectral
analysis of both the K/Al and Si/Al logs, used as
proxies for quartz and illite variation, yielded a major
frequency maximum with a wave length of 0.68 m.
Several spectral peaks of lower power and shorter
wave length are also observed (Figure 6). The ratios
for most of the major peaks of the time series analysis
are nearly identical to those predicted from orbital
theory, if it is assumed that the major peak with a wave
length of 0.68 m is an expression of the 123-ky-long
eccentricity cycle. This assumption is supported by
data from Herbert et al. (1986) and Rose et al. (1996),
who reported results of time-series analyses of Creta-
ceous sediment sequences which also showed a strong
eccentricity signal. The Si/Al log also yielded, in
addition to the spectral peaks that can be assigned to
orbital frequencies, a peak with a wave length of
0.41 m which, if our time assignment is correct,
corresponds to a 74.2 ky signal, as reported from
Cretaceous sediments elsewhere (e.g., Rose et al.,
1996). The only major peak that cannot be assigned
to known orbital frequencies, based on our initial
assumption, is that with a wave length of 0.18 m
(Figure 6) in the results of the time series analysis of Figure 6. Spectral analysis for the K/Al geochemical log
the Si/Al log. Our results make an orbital forcing- (illite proxy) and Si/Al geochemical log (quartz proxy).
The peaks with the highest power can be related to
controlled origin of the observed bedding cycles highly typical Milankovitch frequencies if a sedimentation rate
probable. of 5.53 m/my is assumed. The spectral analysis was
Bralower et al. (1994) reported a best estimate of performed with SPEC-LAB (unpublished shareware
0.6 my for the duration of the OAE 1b for the North program by Guido Port, University of Cologne, based
Atlantic Ocean. In a more recent study Ogg et al. on the Lomb-Scargle algorithm published by Press
et al., 1992).
(1999) estimated 30 ky for the duration of OAE 1b. If
we apply the sedimentation rates estimated by fre-
gen indices increase with organic richness, suggesting
quency analysis to the organic-matter-rich interval of
a higher proportion of marine-derived organic matter
core 19 (316.2–317.4 m), we arrive at 0.217 my
in the organic-matter-rich black shales. This con-
for the duration of the main interval of black shale
clusion is supported by the concurrent increase of the
deposition at Site 417D.
liptinite/inertine+vitrinite ratio with organic-carbon
content (Figure 8B). The liptinites mainly consist of
Organic-matter composition alginite (e.g., dinoflagellate cysts) and liptodetrinite of
uncertain origin. Inertinite and vitrinite phytoclasts
The organic-matter content of the early Albian inter-
are remnants of the terrestrial vegetation, which may
val at Site 417D is highly variable and fluctuates
have experienced several recycling phases prior to final
extensively on the scale of the bedding rhythms (Fig-
deposition. The abundance of dinoflagellate cysts is in
ure 7). TOC values range from 0.03 to 7.12%. The
good agreement with observations of Hochuli & Kelts
black shale intervals of the bedding cycles are enriched
(1979), who recorded dinoflagellate blooms in this
in organic matter, whereas the associated pale to dark
interval. On average, 90% of the observed phytoclasts
green claystones of the interbeds generally contain less
of the black shale members are liptinites. Even the
than 0.5% organic carbon. Most of the organic matter
green clay members contain an average of 45%
is restricted to the stratigraphic interval from 316.20
liptinite.
to 317.40 m, where most of the black shales are
concentrated. The organic matter consists of a mix-
C/S and Fe-TOC-S relationships
ture of marine and terrestrially derived components,
as indicated by hydrogen indices ranging from 22 to The total sulfur content of the sediments ranges from
266 mg HC/g TOC (Figure 8A). Generally the hydro- 0.05 to 1.27% (Figure 7). Microscopic observations
 Geochemical signature and related climatic-oceanographic processes 251

Figure 7. Geochemical log for TOC content, total sulfur content, V/Al, Ni/Al, Cr/Al and Mn/Al ratios. Average shale values
are shown as solid lines (after Wedepohl, 1971). Note the enrichment for vanadium, chromium and nickel in the interval
between 316.20 and 317.40 m and the overall depletion of manganese; see text for discussion. P indicates samples
analyzed for size distribution of framboidal pyrite (see also Figure 10); for key to lithologies, see Figure 2. Black shale
intervals are shaded.

revealed that the main sulfur-containing mineral is
pyrite. The presence of organic-sulfur components
was not investigated and cannot be excluded. Pyrite
occurs both as framboids and finely dispersed in the
mineral matrix. The occasional presence of sphalerite
noted by the Shipboard Scientific Party of Leg 51
(1979) could not be substantiated for the 20 samples
studied by microscopic techniques. The highest sulfur
concentrations occur in the stratigraphic interval with
the highest concentration of black shale, but are not
completely restricted to these intervals (Figure 7). A
C/S cross-plot shows a deviation of both the green
claystones and the black shales from the normal
marine line characteristic for sediments deposited
under oxic conditions as defined by Berner (1984;
Figure 9A). Surprisingly, C/S ratios are lower for the
bioturbated green claystones than for the laminated
black shales, suggesting that sulfate reduction was
more intense in the former than in the shales. Such a
scenario is, however, unlikely because bacterial sulfate
reduction processes require extremely low oxygen
levels to proceed (e.g., Berner, 1984; Raiswell &
Berner, 1985), and the ubiquitous bioturbation indi-
cates at least moderate oxygen supply to the green
claystone intervals. This apparent contradiction can
be resolved if the limitations for pyrite formation in
the section are examined in a Fe-TOC-S diagram
(Dean & Arthur, 1989; Figure 9B). The black shale
samples generally plot along a line extending from the
TOC corner of the diagram to the Fe-S line. This
relationship is typical for sample populations where
pyrite formation is limited by the availability of re-
active iron (Dean & Arthur, 1989; Arthur & Sageman,
1994; Hofmann et al., 1999a, b). Iron limitation
usually occurs in euxinic environments such as
the Black Sea (Raiswell & Berner, 1985; Arthur &
Sageman, 1994), but has also been reported for
Albian organic-matter-rich strata off the coast of West
Africa (Hofmann et al., 1999b). Euxinic conditions
are in good agreement with the observed lack of
bioturbation. The high portion of marine organic
matter still preserved in the black shales suggests that
sulfate reduction continued even after the available
reactive iron was used up for pyrite formation. Thus,
it is probable that some of the H2S generated escaped
from the black shale beds and reacted with the avail-
able iron in the green claystones, leading to low C/S
ratios for this lithofacies. The excess sulfur concen-
trations of this lithofacies are, therefore, thought to be
a function of hydrogen sulfide export from the black
shale intervals rather than of in situ sulfate reduction
processes in the green claystone intervals. Vetö et al.
252 P. Hofmann et al.
Figure 8. A, relationship of hydrogen indices (HI) and
organic-carbon content of samples with a TOC content
>0.5%. Note the shift towards higher HIs with increas-
ing TOC content, indicating successively higher
amounts of marine-derived organic matter. B, liptinite/
vitrinite and inertinite ratio versus organic carbon con-
tent. Note the increase in marine-derived (liptinites)
over terrigenous-derived organic matter with increasing
organic-carbon content.
(1995) estimated that up to 25% of the hydrogen
sulfide produced in non-bioturbated black shales
escaped. We suspect, however, that the percentage
may have been significantly higher in severely iron-
limited systems.
Pyrite size analysis
Euxinic conditions may extend from a few centimetres
above the sediment water interface to more than a
1000 m above, as is currently the case in the Black
Sea. Wilkin et al. (1996) demonstrated that euxinic
Figure 9. A, TOC-total sulfur cross-plot for black shales
(stars) and interbedded bioturbated green claystones.
Note the deviation of both populations from the normal
marine line for oxic sediments (after Berner, 1984). B,
Fe-TOC-S ternary diagram after Dean & Arthur
(1989). The black shale population plots along a line
extending from the TOC corner to the Fe-S line,
indicating formation under euxinic conditions with
limited iron. Symbols as in Figure 8A; for discussion,
see text.
bottom-water conditions can be recognized based on
the size distribution patterns of framboidal pyrites. In
euxinic environments characterized by free H2S in the
water column, pyrite formation begins therein. Pyrites
formed in the water column are, owing to hydro-
dynamic considerations, small and readily transferred
 Geochemical signature and related climatic-oceanographic processes
Figure 10. Discrimination diagram for framboidal pyrite
formed in a euxinic water column (after Wilkin et al.,
1996). The stratigraphic position of the black shales
analyzed is indicated in Figure 7.
to the underlying sediment. Framboidal pyrite popu-
lations that form in sediments with anoxic pore waters
tend to be larger as a result of prolonged periods of
time available for growth. Hence, pyrite framboids in
sediments from euxinic basins are on average smaller
and less variable in size than those from sediments
underlying dysoxic or oxic water columns. Pyrite
size-analysis for nine samples from laminated black
shale intervals in core 19 (Figure 7) show considerable
size variation (Figure 10). These results suggest
that pyrite formation took place mainly in anoxic pore
waters rather than in an extensive euxinic water-
column (Figure 10). Considering the preservation of
sediment lamination in the black shale facies, it seems
probable that euxinic conditions may have extended
to the sediment/water interface; however, an extensive
euxinic bottom-water mass appears to have been
unlikely. The periods of elevated productivity re-
corded from the black shales were insufficient to
generate a cyclic expansion of the oxygen minimum
zone to the sediment/water interface.
Trace-element signature
Redox-sensitive trace elements are known to accumu-
late in concentrations above crustal abundance in
black shales in general and specifically in those de-
posited during OAEs (e.g., Vine & Tourtelot, 1970;
253
Holland, 1979; Brumsack, 1986; Arthur et al., 1990).
Calvert & Pedersen (1993) demonstrated that the
enrichment of selected redox-sensitive trace elements
(e.g. nickel, vanadium, chromium, among others) can
be used to infer sedimentation under anoxic con-
ditions. Trace-element enrichment can occur either in
anoxic basins, where the surface sediments are in
contact with sulfidic waters, or by diffusion from sea
water to anoxic sediments that lie below thin oxic
horizons at the sediment/water interface. Because of
the ambiguity caused by the fact that the metals are
enriched in both situations, only the absence of en-
richment can be used as a reliable guide for oxygen-
ated bottom-water conditions during sedimentation.
Trace-element enrichments can be determined if
their aluminium-normalized concentrations are com-
pared to those encountered in average shale (e.g.,
Wedepohl, 1971), which is considered to be typical
for element patterns of oxic conditions. Element pro-
files for Cr/Al, V/Al, and Ni/Al in core 19 show a
distinct enrichment relative to average shale values for
the black shales between 316.20 and 317.40 m (Fig-
ure 7), suggesting the episodic presence of anoxic
bottom and/or pore waters. The trace-element enrich-
ment of the black shale intervals is, however, signifi-
cantly lower than that recorded for OAE 2 (e.g.,
Arthur et al., 1990), suggesting an event of lower
magnitude than the Cenomanian/Turonian boundary
event. The core intervals above and below the main
interval of ‘black shale’ deposition display ratios simi-
lar to the average shale, including the black shales at
the top of the section and, therefore, show signatures
typical for sediments deposited beneath oxic bottom
waters. Cr, V and Ni concentrations correlate with
TOC content but not with sulfur content (Table 1),
suggesting either absorption or incorporation into the
organic phase (Lewan & Maynard, 1982; Brumsack &
Gieske, 1983; Breint & Wanty, 1991) rather than an
accumulation controlled only by anoxia.
In contrast to the trace metal enrichment reflected
by the Cr/Al, Ni/Al and V/Al ratios, the black shale
intervals generally have low Mn/Al ratios. Manganese
enrichment above the average shale value was only
observed for two samples in the lowermost part of the
profile (Figure 7). In oxic seawater, manganese (II) is
oxidized to insoluble Mn (III) and Mn (IV) oxides,
leading to the accumulation of high manganese con-
centrations in oxic sediments. In sulfidic waters of
anoxic basins, manganese accumulates in its dissolved
state owing to the reduction of Mn (IV) oxides settling
from the oxic waters above. Sediments deposited
under these conditions are characterized by low man-
ganese concentrations. In systems with an oxygen/
sulfide boundary, active manganese recycling occurs
254 P. Hofmann et al.
as a result of reductive solution of manganese oxides
under sulphidic conditions, followed by diffusion
across the redox boundary and subsequent formation
of new manganese oxides (e.g., Calvert & Pedersen,
1993, and references therein). If the cyclic recurrence
of laminated black shales and green bioturbated clay-
stones indicates significant variations in bottom-water
oxygenation, including the episodic presence of exten-
sive euxinic bottom waters, then a high variability in
Mn/Al ratios would be expected. The trace-metal-
enriched black shale intervals, whose lamination pat-
tern, C/S ratios and Fe/TOC/S relationships indicate
deposition under euxinic conditions, should be de-
pleted in manganese. By contrast, the bioturbated
trace-element-poor intervals of the observed bedding
cycles that were deposited under normal marine con-
ditions should be enriched in manganese. This is
obviously not the case (Figure 7). The Mn/Al ratios
are fairly low compared to average shale values for
most of the core interval studied, regardless of sedi-
mentary facies and its inferred oxygenation level (Fig-
ure 7). We believe that Mn-depletion was caused by a
low overall supply of manganese to the sea floor. The
generally low Mn/Al ratios may indicate that manga-
nese was effectively removed from settling particles
elsewhere in the overlying water column. We specu-
late that the presence of an oxygen minimum zone
(OMZ) in shallower waters would have promoted the
release of manganese from settling particles by reduc-
tive dissolution and trapped the dissolved manganese,
thus causing an overall low Mn-flux to the sea floor.
4. Discussion
Climate and sea-level-controlled productivity model for
deposition of black shales
Sediments recovered from core 19 of Site 417D
correspond to the lower M. gracilis radiolarian Zone
and, hence, fall into a time period that has been
reported to be equivalent to the OAE 1b of the early
Albian in the North Atlantic Ocean (Erbacher et al.,
1996, 1999; Erbacher & Thurow, 1997, 1998). The
sediments of this core are characterized by a distinct
organic-matter-rich interval from 316.20 to 317.40 m
that may contain the OAE 1b. It is characterized by
periodically occurring bedding cycles containing
organic-matter-rich black shale intervals. The bedding
cycle members reflect changing productivity and oxy-
genation levels as indicated by organic-carbon con-
tent, kerogen quality, bioturbation and trace element
patterns, C/S ratios and Fe-TOC-S relationships and
are, therefore, interpreted as coupled productivity/
redox cycles. The highest accumulation of organic
matter occurred in the thickest black shale intervals,
suggesting that the intensity of productivity fluctu-
ations reached their peak during this period. The
black shales contain organic matter of marine deri-
vation that must have survived both transport through
a deep water column (3800 m; Sikora & Olsen,
1991) and diagenetic degradation after deposition.
The alteration of the organic matter is recorded by
fairly low hydrogen indices despite a high liptinite
content. The accumulation rate of organic matter in
most of the black shale intervals was sufficient to cause
severe oxygen depletion in the pore waters. This led to
the enrichment of selected redox-sensitive trace ele-
ments above crustal concentrations and also inhibited
the establishment of a bottom-dwelling fauna. Hence,
productivity and preservation of organic matter
were apparently directly linked. The position of the
chemocline separating hydrogen sulfide- and oxygen-
containing waters is, based on the data presented, still
somewhat uncertain and may have either been at the
sediment/water interface or only slightly above it dur-
ing the deposition of the black shale members of the
bedding cycles. An extensive anoxic, bottom-water
body, however, can probably be ruled out because,
based on size analysis, most of the framboidal pyrite
was formed in anoxic pore waters rather than in a
euxinic water column. Therefore, it is unlikely that
an oxygen-minimum zone extended to the sea floor
during ‘black-shale’ deposition. The presence of an
oxygen-minimum zone higher in the water column is,
however, to be expected because of the fairly high
amounts of marine-derived organic matter that sur-
vived transit through the water column. The low
amounts of manganese, regardless of the inferred
degree of oxygen availability recorded in the sediment,
may indicate that manganese was stripped from
settling particles in an OMZ, higher in the water
column, by reductive dissolution.
In contrast, the bioturbated claystone intervals dis-
play characteristics that indicate low productivity and
deposition under normal marine conditions. They
contain low amounts of organic carbon with a higher
terrigenous component, show trace-element patterns
similar to the crustal average, and display C/S ratios
and relationships for Fe, TOC and sulfur typical for
sediments deposited in oxic environments.
The presence of bedding cycles alternating from
bioturbated claystones to laminated black shales sug-
gests a dynamic system which periodically fluctuated
from more oligotrophic to eutrophic conditions, with
high productivity represented by the black shale inter-
vals, to more normal-marine conditions (oligotrophic)
with fairly low productivity represented by the biotur-
bated claystone intervals. The intervals with higher
 Geochemical signature and related climatic-oceanographic processes
nutrient supply and high productivity became more
extensive during the most intense part of the ‘black
shale’ deposition (e.g., Figure 7). However, even
during peak black shale development, the nutrient
supply was insufficient to support a productivity
level high enough to generate permanent eutrophic
conditions in the central North Atlantic.
A suitable model for ‘black shale’ deposition must
consider this dynamic-productivity development. Our
data show a distinct change in the chemical compo-
sition of the clastic fraction of the sediments that
occurred during deposition of the organic-matter-rich
interval between 316.20 and 317.40 m. This chemical
change is also reflected by changes in the mineralogi-
cal assemblage, i.e., the relative abundance of quartz
and the composition of the clay-mineral assemblage.
During ‘black shale’ deposition, reduction of detrital
quartz input took place accompanied by a shift from a
clay-mineral assemblage dominated by illite towards
one dominated more by smectite or I/S mixed-layer
minerals. Periodic higher-frequency fluctuations in
the composition of the clastic source occur on the
scale of the bedding cycles and are reflected in the
Si/Al and K/Al ratios. As shown above, the results of
the spectral analysis may suggest processes related to
orbital forcing for these high-frequency cycles. We
interpret the data set as resulting from the combined
effects of a longer term sea-level rise and subsequent
fall superimposed on short-term climatic variations, as
documented by the Si/Al log. This shift in quartz
content in conjunction with the relative increase in
smectite may reflect the reduced potential for erosion
in flooded continental areas during a rise in sea level.
Short term climatic fluctuations are recorded on the
level of the bedding cycles (Si/Al, K/Al ratios). They
are linked to the nutrient budget of the ocean via the
net rate of precipitation and evaporation, which deter-
mined the degree of weathering, and the transport rate
and transport mechanism of nutrients. In our view, a
rise in sea level raised the overall nutrient supply to
central ocean areas, as predicted by the p-OAE model
of Erbacher et al. (1996), to a point where moderate
fluctuations in the nutrient balance inflicted by the
periodic variations in climate on the surrounding
continents were sufficient to generate productivity
pulses. These pulses are recorded in the black shale
intervals at Site 417D and appear to reflect changes in
climate in northern Africa.
Recent atmospheric general-circulation model ex-
periments have shown that shifts in the regional
precipitation patterns recorded for the early Albian at
Site 417D are most effectively caused by a change in
the land-sea distribution and elevated atmospheric
CO2 levels (e.g., Poulsen et al., 1999). We believe that
255
both mechanisms, a shift in the land-sea distribution
caused by the overall sea-level rise and fall, as well as
fluctuations of the global CO2 budget inflicted by the
periodic burial of organic matter, were effective during
the genesis of black shales at Site 417D.
Because of the existing uncertainty in the dating of
the early Albian black shale deposits at Site 417D,
the exact assignment of OAE 1b to the observed
black shale interval is currently not possible. The
black shales at Site 417D occur, however, in the
stratigraphic interval expected for OAE 1b; their de-
velopment appears to have fallen within a period of
sea-level rise, and was a result of periods of enhanced
productivity in an open ocean environment. The black
shale deposits at Site 417D show, therefore, several of
the characteristics predicted for OAE 1b. We suspect
that if OAE 1b is present at Site 417D and if the
duration of 30 ky for OAE 1b estimated by Ogg et al.
(1999) is correct, it is represented by one of the
thicker black shale beds.
5. Conclusions
The organic matter-rich interval in core 19 at site
417D displays a chemical signature that requires a
combination of processes to explain the genesis of
early Albian black shale deposits. The accumulation
of significant amounts of marine-derived organic mat-
ter in deep-sea environments was probably triggered
by a shift in the overall ocean-wide nutrient balance
caused by a combination of eustatic sea-level rise and
climatic changes on the continents, which altered the
input of nutrients into the North Atlantic Ocean. It
appears that northern Africa and parts of southern
Europe received higher amounts of precipitation dur-
ing this period, suggesting latitudinal shifts in the
major climate belts. This change in climate was prob-
ably caused by atmospheric adjustments in response
to sea-level rise and increasing pCO2. Orbital forcing
for the observed shorter-term climatic modulations is
highly probable.
The black shale deposits at Site 417D show many
characteristics expected for OAE 1b. However, con-
firmation of whether OAE 1b is present at Site 417D
requires improved stratigraphic resolution.
Acknowledgements
This work was supported by a grant of the Deutsche
Forschungsgemeinschaft (DFG, ODP Schwerpunkt
Programm). We thank Ms B. Stapper for technical
assistance and Ms K. Stone for editing several ver-
sions of the manuscript. Reviews by Drs H. Jenkyns
and J. Erbacher helped to improve the manuscript.
256 P. Hofmann et al.
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