Earth-Science Reviews 95 (2009) 63–96

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Earth-Science Reviews
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 / e a r s c i r ev

A marine biogeochemical perspective on black shale deposition

D.Z. Piper a,⁎, S.E. Calvert b
a
US Geological Survey, M/S 901, Menlo Park CA., 94025, United States
b
University of British Columbia, Vancouver B.C., Canada V6T 1W5

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

Article history: Deposition of marine black shales has commonly been interpreted as having involved a high level of marine
Received 22 November 2007 phytoplankton production that promoted high settling rates of organic matter through the water column and
Accepted 11 March 2009 high burial fluxes on the seafloor or anoxic (sulfidic) water-column conditions that led to high levels of
Available online 28 March 2009
preservation of deposited organic matter, or a combination of the two processes. Here we review the
hydrography and the budgets of trace metals and phytoplankton nutrients in two modern marine basins that
Keywords:
black shales
have permanently anoxic bottom waters. This information is then used to hindcast the hydrography and
trace elements biogeochemical conditions of deposition of a black shale of Late Jurassic age (the Kimmeridge Clay
marine geochemistry Formation, Yorkshire, England) from its trace metal and organic carbon content. Comparison of the modern
Kimmeridge Clay and Jurassic sediment compositions reveals that the rate of photic zone primary productivity in the
Kimmeridge Sea, based on the accumulation rate of the marine fraction of Ni, was as high as 840 g organic
carbon m− 2 yr−1. This high level was possibly tied to the maximum rise of sea level during the Late Jurassic
that flooded this and other continents sufficiently to allow major open-ocean boundary currents to penetrate
into epeiric seas. Sites of intense upwelling of nutrient-enriched seawater would have been transferred from
the continental margins, their present location, onto the continents. This global flooding event was likely
responsible for deposition of organic matter-enriched sediments in other marine basins of this age, several of
which today host major petroleum source rocks.
Bottom-water redox conditions in the Kimmeridge Sea, deduced from the V:Mo ratio in the marine
fraction of the Kimmeridge Clay Formation, varied from oxic to anoxic, but were predominantly suboxic, or
denitrifying. A high settling flux of organic matter, a result of the high primary productivity, supported a high
rate of bacterial respiration that led to the depletion of O2 in the bottom water. A high rate of burial of labile
organic matter, albeit a low percentage of primary productivity, in turn promoted anoxic conditions in the
sediment pore waters that enhanced retention of trace metals deposited from the water column.
Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2. Setting the stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.1. The problem of temporal scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.2. Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.3. Water-column versus sediment redox. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.4. Nutrient sources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.4.1. Fluvial nutrient source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.4.2. Groundwater nutrient source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.4.3. Atmospheric nutrient source. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.4.4. Oceanic nutrient sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.5. Trace-element sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.5.1. Lithogenous trace-element source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.5.2. Seawater trace-element sources, trace nutrients and redox-sensitive trace metals . . . . . . . . . . . . . . . . . . . . . . . 72
2.5.3. Trace-element accumulation rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
2.5.4. Limitations of modeling trace-element ratios and accumulation rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

⁎ Corresponding author. Tel.: +1 650 329 5187; fax: +1 650 329 5491.
E-mail address: dzpiper@usgs.gov (D.Z. Piper).

0012-8252/$ – see front matter. Published by Elsevier B.V.

doi:10.1016/j.earscirev.2009.03.001
64 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96

3. Modern marine environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

3.1. The Cariaco Basin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.1.1. Oxidant balance in and residence time of bottom water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.1.2. Trace-metal budgets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.2. The Black Sea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.2.1. Primary productivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.2.2. Oxidant balance in bottom waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.2.3. Bottom-water residence time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.2.4. Trace-metal budgets in bottom waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.3. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4. An ancient marine environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.1. General description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4.2. Lithogenous- and marine-sediment fractions: A trace-element partitioning model . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.3. Biogenous sediment fraction: Primary productivity and rate of upwelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.4. Hydrogenous sediment fraction: water-column redox and residence time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.5. Hydrography of primary cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
5. Summary and conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

1. Introduction
Black shales are major source rocks for oil deposits, commonly
contain economically viable phosphate deposits, and can host a
variety of trace elements that are potentially highly toxic, making a
study of these deposits both economically and environmentally
important. As indicated in several recent reviews of their environ-
ments of deposition (Tyson and Pearson, 1991; Arthur and Sageman,
1994; Wignall, 1994; Harris, 2005), both the organic enrichment and
generally high contents of trace and minor elements that form
insoluble sulfide phases, or that are reduced under sulfidic condi-
tions (Vine and Tourtelot, 1970; Gustafson and Williams, 1981; Jacobs
et al., 1985, 1987; Crusius et al., 1996), have been ascribed to accu-
mulation in basins that had anoxic bottom waters. This condition
is often conjectured to have been maintained by a stratified water
column that isolated the photic zone from the bottom-water nutrient
reservoir (Hatch and Leventhal, 1992; Turner, 1992; Ettensohn, 1995;
Wignall and Myers, 1988). Contrary to this interpretation, the organic
richness of many black shales has led some geologists to conclude
that they were deposited under conditions of high primary pro-
ductivity, together with a relatively low degree of dilution of the
organic matter by siliciclastic and skeletal, largely planktonic, debris
(e.g., Lallier-Vergès et al., 1995; Herbin et al., 1995; Perkins et al.,
2008).
Scenarios for the control of productivity and for the maintenance
of anoxic depositional conditions are highly diverse. Most rely on, or
make assumptions about, processes and conditions in the modern
ocean. Thus, a firm understanding of basic oceanographic processes is
required if explanations of black shale formation are to be based on
uniformitarian principles. Such understanding should constrain
conditions of black shale deposition and advance our overall knowl-
edge of the factors that led to the formation of this important lithology
that occurs repeatedly through geological time. While recognizing
that reworking and redeposition of sediment, chemical alteration
during and following burial, and surficial weathering following uplift
and exposure all may mask and, in some cases, erase the original
geochemical signal of deposition, application of modern oceano-
graphic principles and the geochemistry of modern marine deposits
demonstrate that several currently held interpretations of black shale
accumulation need to be re-examined.
In this review, we adopt a three-fold approach to examine
explanations of black shale formation that invoke former levels of
phytoplankton production and bottom-water oxygen depletion. In
the first part, we review nutrient and trace-element sources and
cycles in modern marine basins. Several paleoceanographic scenar-
ios have been constructed that make it difficult to advance falsifiable
hypotheses for black shale formation and, in many cases, lead to
untenable conclusions. These include (1) the supply of nutrients to
marine environments by rivers to account for the enrichment of
organic matter (i.e., high primary productivity) in sediments that
accumulated under bottom-water O2 depletion, where sub-surface
waters and their nutrient inventory were supposedly isolated from
the photic zone; (2) the isolation of anoxic bottom waters to explain
diverse occurrences of organic enrichment in sedimentary
sequences (Woolnough, 1937; Brockamp, 1944; Demaison and
Moore, 1980) even though in many deposits sedimentological and
paleontological evidence points to the presence of oxygenated to
denitrifying or, at least ventilated conditions at the seafloor; and
(3) the assumption that high concentrations of organic matter in
these deposits equate to a high degree of its preservation relative to
primary productivity.
In the second part, we present a quantitative analysis of organic
matter and trace-element fluxes to the seafloor in two modern anoxic
basins—the Cariaco Basin and the Black Sea—that provides insight
into the relationships between the hydrography, surface-water
primary productivity, and bottom-water redox conditions of the
two basins, and the eventual accumulation of trace elements and
organic matter on the seafloor. The results establish sedimentary
trace-element proxies for these three important properties of the
water column.
In the final section, we apply this analysis to an examination of
oceanographic conditions that prevailed during deposition of the
extensively studied Late Jurassic Kimmeridge Clay Formation (KCF) of
western Europe (Cox and Gallois, 1981; Wignall, 1990; Herbin et al.,
1995; Tyson, 1996; Tribovillard et al., 2005), focusing mainly on the
geochemistry of samples from three cores from the Cleveland Basin,
Yorkshire, England (Fig. 1), but with reference to the geochemistry of
samples from outcrops of age correlative formations of the Boulonnais
Basin in northern France.
We adopt a uniformitarian approach that focuses on oceanographic
processes rather than attempting to advance unique paleogeographic
models for ancient sedimentary basins. Although we examine the
biogeochemical processes in the shallow-silled and largely isolated
Cariaco Basin and Black Sea, we recognize that they may not be
appropriate bathymetric models for basins in which black shales
accumulated in the geologic record. Indeed, our analysis suggests
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 65

Fig. 1. Paleogeographic map of the Late Jurassic Kimmeridge Sea, Western Europe, showing the locations of the two sites sampled for chemical analysis. Chemical analyses were made
available by N. Tribovillard. The map is adapted from Herbin et al. (1995). For a presentation of the bathymetry during the Late Jurassic see Ziegler (1990).

just that. However, understanding the hydrographic, chemical, and on the deposition of the Kimmerdigian organic- and metal-enriched
biological processes of the water column in these modern envi- shales that accumulated from vast, perhaps non-silled and relatively
ronments helps to unravel the geochemical and hydrographic controls shallow, epeiric seas.
66 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96

2. Setting the stage
2.1. The problem of temporal scales
Equal thicknesses of modern sediments and ancient rock strata
represent different time intervals, owing to effects of sediment com-
paction as well as the possible incompleteness of the rock record. The
geochemistry of black shale samples commonly represents conditions
that might have extended over several hundred to even thousands of
years, owing to constraints of sampling and sediment accumulation
rates, whereas modern sediments can be sampled on a scale of less
than a year to decades. For example, in cores recovered from the
Cleveland Basin (Herbin et al., 1995; Tribovillard et al., 2005), the part
of the section of the KCF that extends from the top of the Mutabilis
ammonite zone to the top of the Wheatleyensis zone is as much as
130 m thick (Fig. 2) and represents a time interval of 2.8 to 4 My

Fig. 2. Stratigraphic section of the Kimmerdige Clay Formation in Yorkshire, England (the Cleveland Basin) and of correlative formations at Cap de la Crèche, northern France (the
Boulonnais Basin), adapted from Herbin et al. (1995). The five organic-carbon-rich intervals (ORIs) in the Yorkshire area are based on the distribution of Corg. Their positions at the
Cap de la Crèche site are based largely on paleontologic correlations with the section in Yorkshire, rather than on the actual distribution of Corg (Herbin et al., 1995). Uncertainty of the
positions of the ORIs at this site is depicted by the broken symbols. For the purposes of this paper, the intervening intervals are referred to in the text as organic-poor intervals (OPIs),
each occurring immediately below the corresponding numbered ORI.
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 67

(Gradstein et al., 1995, 2004). We have adopted an interval of 3.6 My
(Weedon et al. (2004), which yields the following sedimentation rate:
Sediment accumulation rate = 13; 000 cm
3:6 my
−1
= 0:0036 cm yr :
Each 1 cm thick sample represents 280 years of deposition,
severely averaging the geochemical conditions of deposition that may
have changed on time scales of decades or even seasons. At an average
density of 2.3 g cm− 3 (Weedon et al., 2004), the mass accumulation
rate was 83 g m− 2 yr− 1.
2.2. Definitions
We adopt the following definitions and terminology to categorize
marine environments having different dissolved oxygen concentra-
tions. The boundaries of oxygenation regimes (Fig. 3) are set by the
sequential microbially-driven oxidation reactions that degrade
organic materials in marine waters and sediments (Breck, 1974).
Oxygen is the major oxidant in all surface marine waters that are in
equilibrium with the atmosphere, and in sub-surface waters and
sediment pore waters where oxygen is above a concentration of ca.
50 μM (Berner, 1981). Within the range of 50–300 µM (depending on
temperature) organic detritus will be oxidized by oxygen as the
terminal electron acceptor under oxic conditions. Trace elements that
accumulate from seawater (i.e., not including the generally dominant
fraction incorporated in aluminosilicate lattices) as oxides under this
redox condition include Fe, Mn (Fig. 3), and several trace elements
adsorbed by the oxyhydroxides of these two metals (Nameroff et al.,
2002). However, Fe and Mn are the critically diagnostic elements.
ð1Þ Suboxic conditions are defined by the depletion of oxygen below ca.
50 μM, but prior to the onset of SO2−
4 reduction (Richards, 1975; Glazer
et al., 2006), when dissolved NO− 3 and the remaining O2 act as the
major terminal electron acceptors. Solid oxyhydroxides of Mn, Fe, and
Ce and dissolved species of Cr, Re, U, and V act as trace, subordinate
electron acceptors (Fig. 3). The latter four metals are reduced to less
soluble ionic states than under oxic conditions and eventually
accumulate on the seafloor. Because of the much lower concentration
of NO− 3 in seawater and, hence, the narrow redox range over which it
is the dominant electron acceptor, suboxia may not have been
considered significant in the geological record. However, it is the
dominant redox condition under which: (1) the essential and, in many
areas of the ocean, limiting nutrient NO− 3 is lost from the dissolved
fixed-N pool (N2O, NH3, NO− −
2 , and NO3 ) in seawater (Codispoti, 1989),
(2) carbonate-fluorapatite accumulates (Burnett and Froelich, 1988),
and (3) several major sedimentary phosphorite deposits (Fonseca,
2000; Piper, 2001) and black shales may have accumulated in the past
(Perkins et al., 2008). Anoxic conditions ensue when the reservoirs of
these other oxidants have been essentially exhausted and H2S is
produced by SO2− 4 reducing bacteria (H2S is used throughout the
paper to refer to all forms of dissolved sulfide). Apparent reduction of
MoO2− 4 and Cu2+ and their accumulation on the seafloor, along with

Fig. 3. Schematic representation of bacterial respiration versus water-column depth in marine basins experiencing O2 depletion in the bottom water. Profiles of O2, NO− −
3 , NO2 , NH3
(NH3 plus NH+ 4 ) and H2S (all forms of dissolved S
2−
) concentrations are representative of all anoxic basins, with depths, zonal thicknesses, maximum oxidant concentrations varying
from basin to basin. Maximum values for each in the Cariaco Basin are ca. O2 210 μM, NO− −
3 12 μM, NO2 0.1 μM, H2S 40 μM, and NH3 15 μM (Richards, 1975). Half-cell redox reactions are
shown for the major electron acceptors. The different colors are intended to identify the oxic photic (light blue) and aphotic zones (dark blue), suboxic zone (orange), and anoxic
zone (green). Approximate thicknesses of redox zones in various modern basins depleted in O2 at depth are as follows: oxic (50–150 m), suboxic (50–150 m), and anoxic (200 to
2100 m). Stabilities of trace-element species under the different redox conditions are shown in the center, calculated from thermodynamic constants (see Piper, 2001). In the case of
Cr, it precipitates possibly as Cr(OH)3, or is adsorbed onto settling particles, under mildly denitrifying to anoxic conditions, i.e., throughout the O2 depleted region of the water
column. Under oxic conditions, Cr is in the oxidized and more soluble CrO2− 4 valence state (Murray et al., 1983). MnO2 responds oppositely; it is reduced to a soluble valence state
(probably Mn2+) under anoxic conditions, but is stable within the oxic realm. Depths of several modern basins are shown at far right, together with the estimated depth of the
Jurassic Cleveland Basin. Redox conditions in the water columns of each are given by the vertical lines, for which the broken lines represent temporally varying redox conditions in the
bottom waters.
68 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
the reduced species of Cr, Re, U, and V and precipitates of FeS, CdS and
ZnS (Fig. 3) characterize this level of bacterial respiration (Jacobs et al.,
1985, 1987).
Other terms have been used to describe oxygenation regimes
in marine environments (Tyson, 1987). Dysoxic conditions have
been defined for environments where dissolved oxygen levels are
ca. 10–100 µM, encompassing much of the suboxic range defined by
the geochemistry of the deposit. Dysoxic conditions equate to the
dysaerobic biofacies. Hypoxic conditions are normally used to describe
variably reduced concentrations of dissolved oxygen that cause stress
in aquatic organisms. These finer-scale distinctions have been erected
on the basis of distinctive benthic faunal assemblages rather than the
presence/absence of specific electron acceptors. The use of the suffix
aerobic is confined to the physiology of the organism or consortium
that utilizes a particular oxidant. Exaerobic is also used as a biofacies
term for environments where shelly macrofauna are found on anoxic
sediment surfaces that are not bioturbated, and where oxygen levels
in the bottom water and surface sediment pore water are ca. 5–10 µM
(Savrda and Bottjer, 1987). Thus, aerobic, dysaerobic and anaerobic
facies equate to oxic, suboxic, and anoxic regimes (Tyson and Pearson,
1991). The latter are more useful for geochemical studies of sediments
as they are defined uniquely by the suite of trace elements that
accumulates on the seafloor under the specific redox conditions of the
bottom water. The term euxinic (Black Sea-like, from the Greek Pontos
Euxinus; King, 2004), commonly used in the geological literature, is
used to depict sulfidic bottom waters as distinct from those situations
where sedimentary pore waters are anoxic (sulfidic) but measurable
oxygen is found in the bottom waters (Berner, 1981). Tyson (1995)
suggests that anoxic be used to describe sulfidic bottom-water
conditions, which we adopt.
2.3. Water-column versus sediment redox
The attribution of preferential organic matter accumulation in
ancient rock sequences to anoxia frequently fails to distinguish
explicitly between paleoceanographic settings where the bottom
water of a basin is anoxic, and therefore the surface sediments
themselves are anoxic, and where bottom water immediately above
the sediment/water interface is suboxic or even oxic, but the sediment
pore water is anoxic (Tourtelot, 1979). Examples of the first scenario
are found in several well-known basins characterized by a physical
barrier, which restricts bottom-water renewal or ventilation, such that
the oxygen content of the bottom water becomes depleted when the
supply rate of reduced (organic) carbon exceeds the flux of oxygen
from outside the basin. Bacterial respiration within the basin water
(Fig. 3) is driven first by aerobic metabolism of settling organic debris
using oxygen as a terminal electron acceptor, followed by NO− 3 the water column depends on the balance between the supply of the
reduction, and finally SO2− 4 reduction. This depth sequence is
observed in the water column of all basins in which anoxic conditions
are present in the bottom water (Glazer et al., 2006).
The oxygen minimum zone (OMZ) in some areas of the modern
ocean has dissolved O2 contents that are a few percent of surface-
water concentrations (Karstensen et al., 2008), which remain
oxygenated due to near-surface photosynthesis and gas exchange
with the atmosphere. The low oxygen conditions at depth are con-
trolled by the rate of lateral intermediate water circulation (Wyrtki,
1962), balanced against the rate of bacterial respiration, which is
determined by the settling flux of organic matter from local surface
waters and much less so from local river sources (see Section 2.4.1).
Extensive areas in the eastern tropical Pacific, the Arabian Sea, and the
southeastern Atlantic have dissolved O2 concentrations b5 μM; these
waters are suboxic (Codispoti, 1980; Murray et al., 1983; Codispoti
et al., 2001; Nameroff et al., 2002; Kuypers et al., 2005; Morford et al.,
2005). Hydrogen sulfide has been reported in some OMZ (Ivanenkov
and Rozanov, 1961; Dugdale et al., 1977), but anoxic conditions in the
open ocean are rare.
The establishment of redox conditions in modern marine sedi-
ments depends on the settling flux of particulate organic matter to the
seafloor and its rate of burial (Canfield, 1989, 1994). The settling flux
through the water column decreases with water depth (Suess, 1980;
Pace et al., 1987; Thunell et al., 2000; Goñi et al., 2003), such that a
high burial flux of organic carbon (Corg), relative to primary
productivity, is only possible at seafloor depths of roughly hundreds
of meters versus thousands of meters that characterize the pelagic
environment. Within modern sediment, the boundary between oxic
and anoxic zones varies from less than a millimeter to greater than
15 cm below the seafloor when progressing from coastal embayments,
to the continental shelf, to the upper slope, and finally to the lower
continental slope.
The oxic–anoxic boundary, based on Eh measurements and trace-
element inventories (Bonatti et al., 1971), is further defined by a color
change from dark brown at the surface to light green at depth (Lyle,
1983). In many shallow sea-floor environments, intensely anoxic
conditions (high dissolved sulfide in the pore waters) are commonly
observed at or within a few millimeters of the sediment–water inter-
face, above which fully oxic conditions prevail. Bonatti et al. (1971)
reasoned that increasing rates of bulk-sediment accumulation from
lower slope to shallow shelf allowed for increasing burial rates of
labile organic matter in nearshore settings. A decreasing flux of
organic matter to the seafloor, owing to a decrease in primary
productivity away from the coast (Mullin, 1986) and increasing ocean
depth (Suess, 1980), also contribute to this change. Organic matter is
further degraded during burial (Dean and Gardner, 1998), but largely
in the uppermost centimeters under the redox conditions of the
bottom waters (Jørgensen, 1982). Where sediment accumulation
rates are high, a relatively large fraction of labile organic matter
escapes oxidation at the very surface (Canfield, 1989, 1994; Betts and
Holland, 1991). Its oxidation at depth in the sediment depletes the
pore waters of residual O2, NO− 3 , and Mn/Fe oxyhydroxides, thereby
promoting SO2− 4 reduction near and even at the sediment surface.
Under this condition, organic matter accumulates (is buried) under
anoxic conditions, but was deposited under oxic water-column con-
ditions. Although the sediments in this situation accumulate beneath
an oxic water column, they may contain mineral phases, e.g., pyrite, or
elemental species that can only form or be fixed under low redox
potentials. They are therefore archives of accumulation under anoxic
conditions. The distinction between water-column and sediment
pore-water anoxia is critically relevant to any discussion of the envi-
ronment of formation of black shales, in view of the emphasis com-
monly placed on anoxic water-column environments as a necessary
condition for the formation of this facies.
Maintenance of the different conditions of bacterial respiration in
reductant Corg and the oxidants O2, NO− 2−
3 , and SO4 . As described
previously, O2 is utilized by bacteria in the remineralization of Corg.
Oxygen is supplied by mixing of near-surface and deeper waters and
by the sinking and lateral flow of oxygenated waters below the near-
surface waters. Vertical mixing is often severely inhibited by the
vertical density stratification of ocean waters, in turn controlled by
vertical gradients of temperature and salinity. The lateral circulation,
or advection, of water along constant density (isopycnal) surfaces is a
more important mode of intermediate and bottom-water ventilation.
An illuminating example of advection is found on the continental
margin of Peru, where the poleward Peru Undercurrent injects
oxygenated seawater across the seafloor within the OMZ where it
impinges on the outer shelf and upper slope. Although bottom-water
oxygen concentrations are a few micromolar, the vigorous flow of
this water, albeit with very low O2 concentrations, maintains a robust
macrofaunal community (Arthur et al., 1998). Likewise, oxygen is
injected into shallow intermediate anoxic waters in the Black Sea as
manifested by the interleaving of water with hydrographic properties
distinct from the ambient water (Murray et al., 1991; Özsoy et al.,
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 69

1991; Grégoire and Stanev, 2001; Özsoy et al., 2001; Murray et al.,
2007).
The occurrence of pyrite in black shales has often been used as
evidence for their accumulation under anoxic bottom-water condi-
tions (e.g. Berry et al., 1989; Buggisch, 1991; Suzuki et al., 1998;
Caplan and Bustin, 2001; Galeotti et al., 2003; Martinez, 2003). While
sulfidic conditions are required for pyrite formation (Berner, 1970),
the process can occur in sediments that accumulate under fully
oxygenated water columns as well as in anoxic basins (Goldhaber and
Kaplan, 1974; Goldhaber et al., 1977). Thus, fine-grained shallow-
water marine sediments characteristically have relatively high
pyrite contents, especially where settling fluxes of organic matter
are high due to high productivity and shallow depths (Suess, 1980).
The concentration of this authigenic phase commonly correlates
strongly with Corg content due to organic matter limitation of post-
depositional sulfide production. The occurrence of pyrite in black
shales should not, therefore, be used as an indicator of a sulfidic
(anoxic) basin.
The Corg:Spyrite ratio has also been used to infer an anoxic water
column in the geological record. This proxy, developed by Leventhal
(1983) using data from recent Black Sea sediments published by Hirst
(1974), noted an intercept on the S-axis in the regression of total S
versus Corg, in contrast to data from “normal” marine sediments sensu
Berner (1982) that are anoxic but accumulate beneath oxic waters.
Pyrite, i.e. S, enrichment was attributed to the presence of H2S in the
water column of the Black Sea as well as the sediment pore waters.
The systematics of this additional or syngenetic pyrite versus the
diagenetic pyrite that forms in the sediment has been examined by
Raiswell and Berner (1985). On the basis of these results, low Corg:S
ratios have become a common criterion to identify anoxic water-
column conditions in the geological record (e.g. Leckie et al., 1990;
Jones and Manning, 1994). Subsequent work on Black Sea sediments
(Calvert and Karlin, 1991; Lyons and Berner, 1992), however, has failed
to replicate the high S values reported by Hirst (1974). The more
recent work shows that the data for Late Holocene sediments of
the Black Sea have higher Corg:Spyrite ratios than “normal” marine
sediments, with no intercept on the S-axis. Moreover, data from the
anoxic basins of the Baltic Sea (Boesen and Postma, 1988) and the
Cariaco Basin (Lyons et al., 2003) also show no systematic S enrich-
ment relative to Corg compared with “normal” marine sediments. In
addition, the sediments accumulating on the continental margins of
Peru, Namibia and Oman, which are bathed in low oxygen waters of
the OMZ, also have much higher Corg:Spyrite ratios than “normal”
marine sediments (Morse and Emeis, 1990; Suits and Arthur, 2000).
The lack of S enrichment under these conditions is due to Fe limitation
during pyrite formation (Lyons and Berner, 1992), owing to the limited
burial of easily reducible solid-phase Fe in siliciclastic minerals and
oxyhydroxides, in the latter case because of their reduction to soluble
Fe2+ in the overlying suboxic and anoxic waters. The proposition that
sediments accumulating in basins with sulfidic water columns have
distinctively different Corg:S ratios from those sediments that are
oxygenated at the sediment/water interface but anoxic at depth is not
supported by these more recent observations.
2.4. Nutrient sources
Most primary production in the ocean is confined to near-surface
waters, where sufficient light is available for photosynthesis. A minor
site of production on a global scale is found in the deep ocean around
hydrothermal vents, where the H2S/SO2− 4 system provides an energy
source (van Dover, 2000). The utilization of essential nutrients
(various chemical species of N, P, Si, and several trace nutrients)
during phytoplankton growth depletes their concentrations to low
levels over most of the ocean surface (Fig. 4). Regeneration of the
nutrients occurs in sub-surface waters when particulate organic
matter settles into deeper waters, resulting in the nutrients extracted
from the near-surface waters increasing in concentration below the
photic zone. They are only very weakly utilized by bacteria in the
deeper water. Sustained primary production is only possible when
and where nutrients are re-supplied to the surface layers, either from

Fig. 4. Depth profiles of O2, major nutrients, and trace elements in the central North Pacific Ocean. The O2 minimum in the far eastern Pacific is an order of magnitude shallower and an
order of magnitude more intense than shown here and is one of several sites in the open ocean that experiences denitrification in the water column. Except for Mo, the trace elements
exhibit a nutrient-type profile. The uptake of V by algae is discernable, albeit weakly, by its slight depletion in the photic zone (Collier, 1984). For Mo, its high concentration in
seawater (Collier, 1985) and weak uptake by algae (Brumsack, 1986) mask any possible biological depletion in the photic zone and concomitant enrichment at depth via release from
organic matter through the oxidation of settling organic matter.
70 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
land runoff, groundwater flow, atmospheric deposition, or from the
vertical movement and mixing of sub-surface waters into the surface
photic layer of the ocean.
2.4.1. Fluvial nutrient source
The limitation of marine production by the supply of nutrients to
the photic zone, due to strong water-column stratification as is found
in anoxic basins, has commonly led to the attribution of a dominantly
fluvial nutrient input to a sedimentary basin to explain the high
organic content of some black shales (Baird and Brett, 1991;
Ettensohn, 1995). Terrestrial rocks and soils are the ultimate sources
of the nutrients phosphate and silica (HPO2− 4 and H4SiO4 at sea water
pH), which are delivered to the ocean in dissolved forms via rivers.
Although some N is also supplied to the ocean via rivers, the principal
source of N to the ocean is from the fixation of N2 by diazotrophic
cyanobacteria within the ocean (Karl et al., 2002). Nitrate (NO− 3 ),
the main form of fixed-N in the open ocean, is produced by
the remineralization of organic-N via the oxidation of NH3 (nitrifica-
tion) liberated from proteins. Thus, the cycles of N and P, the two
macronutrients essential for phytoplankton growth, are de-coupled.
Dissolved Fe also limits primary production in some oceanic
regions that have unutilized nutrients in the photic zone. It is a co-
factor in the enzyme NO− 3 reductase, required by phytoplankton cells
to reduce NO− 3 to ammonium before incorporation in protein syn-
thesis. Large areas of the Southern Ocean, the Subarctic and equatorial
Pacific, the so-called High Nutrient Low Chlorophyll (HNLC) regimes
of the open ocean, have inadequate Fe supplies either from deeper
waters, coastal lands, rivers, or bottom sediments, relative to the
supplies of NO− 2−
3 and HPO4 . Efficient utilization of the ambient
nutrients (Martin, 1991, 1992) is limited, owing to Fe precipitation as
an oxyhydroxide in the presence of oxygen, which effectively removes
it from seawater. Several coastal regions also have HNLC character-
istics, as off northern California (Hutchins and Burland, 1998) and
Peru (Hutchins et al., 2002).
Available information on the impact of fluvial runoff on ocean
production suggests that the stimulation of production by this source
is confined to estuaries or to fairly restricted areas of the coastal ocean.
In the case of the Amazon River, which is responsible for approxi-
mately 18% of the global fresh-water runoff to the ocean (Gibbs, 1967)
and is affected only to a minor degree by anthropogenic nutrient
additions, most of the dissolved fixed-N and HPO2− 4 carried by the
river is removed within and immediately off the river mouth when
most of the suspended load has been deposited and sufficient light
penetration into the waters promotes estuarine algal production
(Edmond et al., 1981; DeMaster et al., 1996; Smith and DeMaster,
1996). Between 25 and 60% of the river-borne dissolved silicon is
removed by the growth of diatoms also within the river plume
(Milliman and Boyle, 1975; DeMaster and Pope, 1996; DeMaster et al.,
1996). Although high production rates characterize the shelf waters
close to the Amazon River mouth due to a combination of fluvial and
offshore nutrient supplies (see Section 2.4.4), the low-salinity waters
flowing northwards along the coasts of Brazil and the Guyanas are
severely depleted in nutrients (Ryther et al., 1967; DeMaster et al.,
1996). Coastal production is seasonally higher than it is offshore, but it
results from upwelling (see Section 2.4.4) of nutrient-enriched
marine waters between the coast and the Amazon plume. This is
due to the divergence of surface waters (Ekman transport) away from
the coastal barrier during summer (Gibbs, 1980; Geyer et al., 1996),
when the Intertropical Convergence Zone (ITCZ) lies north of the
equator (Haug et al., 2001), causing the southeast trade winds to blow
along the coastline. Although fluvial sources of surface waters
probably derived from the Amazon and Orinoco Rivers can be
detected in the western tropical Atlantic (Müller-Karger et al.,
1989b) and the Caribbean (Moore et al., 1986; Müller-Karger et al.,
1989a; Bonilla et al., 1993), production in these areas is largely
confined to frontal regions and is based entirely on nutrients recycled
in the plume regions and supplied from upwelling of water below the
surface fresh-water plumes (Corredor et al., 2003).
Nutrient delivery to the Atlantic by the Zaire River also appears to
have only a modest impact on production in the coastal region off
western Africa. Production is lowest within the offshore region where
salinities show a 50/50 mixture of river water and seawater (Cadée,
1978). It is highest at zero salinity and at normal salinity, i.e.,
undiluted, offshore seawaters. The higher offshore production is due
once again to coastal upwelling, which is highest in summer (van
Bennekom et al., 1978) when the eastern boundary surface Benguela
Current is strongest, with the Coriolis component of flow (Ekman
transport) offshore to the west, or to the left of the direction of the
dominant flow (Southern Hemisphere).
Nutrient levels in estuaries are often higher in waters at intermediate
salinities than in either the river or the offshore end members. This well-
known phenomenon reflects the two-layer estuarine flow of the waters
and the recycling of nutrients between particulate and dissolved forms.
Organic debris that falls into deeper waters can be retained within the
estuary as a consequence of the compensating return flow of water from
offshore below the out-flowing fresher surface waters. Remineralization
of this organic matter releases nutrients to the dissolved inventory,
leading to their accumulation in the inflowing seawater below the
surface flow. Such recycling causes estuaries to be nutrient traps
(Redfield et al., 1963), or filters. Entrainment of deeper waters into the
out-flowing surface waters at the boundary between the two opposing
flows enriches the surface sun-lit waters with the regenerated nutrients
and with nutrients transported into estuaries from offshore, resulting in
estuaries often being much more productive than open-ocean regimes.
For example, surface water fixed-N, together with organic-N and HPO2− 4
concentrations in the Amazon River estuary are highest at salinities
between 2 and 8‰ compared with the river end-member and offshore
waters at oceanic salinity (Edmond et al., 1981). Other major estuaries,
such as the Zaire (van Bennekom et al., 1978), the St. Lawrence (Coote
and Yeats, 1979), and the Changjiang (Edmond et al., 1985), are similarly
enriched in nutrients at intermediate salinities. In some estuaries, the
process of entrainment can supply significantly more nutrients from
offshore than that delivered by the river itself (Yin et al.,1997). Estimates
of the supply of nutrients to the continental margin of the North Atlantic
show that large rivers and estuaries currently supply only around 10–
15% of the total (dissolved and particulate) fixed-N and HPO2− 4 to the
shelf region, whereas the offshore supplies 80–90% (Nixon et al., 1996).
The larger offshore oceanic nutrient supply is due to the estuarine
circulation of most shelf systems; low-salinity surface water flows
offshore to be replaced by nutrient-rich deep water that is sourced
beyond the shelf break (Iselin, 1939; Hseuh and O'Brien, 1971;
Wroblewski and Hofmann, 1989). This process, as noted earlier, even
leads to the import of deep-water nutrients into the surface plumes of
rivers (Geyer et al., 1996). In the Amazon, that supply is 5- to 10-fold
greater than the supply from the river itself (DeMaster and Pope, 1996).
Despite the high productivity of shelf waters off the Amazon River
that is only partly due to fluvial nutrient supply, the sediments of the
shelf affected by the river plume are composed mainly of terrigenous
silty clays carried to the shelf predominantly in suspension (Kuehl
et al., 1996; Sternberg et al., 1996). The organic matter and biogenous
silica produced in the river plume and deposited on the shelf are
rapidly remineralized in the strongly reworked bottom sediments
(Aller et al., 1996) and diluted by the high lithogenous background;
Corg contents of the sediment are b1% by weight (Aller and Blair,
1996), with as much as 70–90% of terrestrial origin (Showers and
Angle, 1986; Sommerfield et al., 1996). Thus, as is the case in large
river deltas and their offshore extensions, most of the organic matter
is derived from the land rather than having a marine source (Berner,
1982; Hedges and Keil, 1995).
We have avoided a discussion of an anthropogenic input of
nutrients to rivers, although this is an important source currently that
can lead to major environmental problems, particularly in coastal
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
areas (e.g., van Bennekom et al., 1975; Maybeck, 1982; Halim, 1991;
Rabalais et al., 1996; Lancelot et al., 1997).
2.4.2. Groundwater nutrient source
Groundwater seepage also supplies fixed-N and HPO2− 4 to estuarine
waters and directly to coastal regions (Johannes, 1980; Capone and
Bautista, 1985; Giblin and Gaines, 1990; Varela et al., 1990). This source
has become more important in recent decades owing to contamination
of groundwaters by municipal and agricultural runoff (Nolan and Stoner,
2000). However, groundwaters are also enriched in nutrients even in
undisturbed forested watersheds (Ford and Naiman, 1989) so that this
source was probably important prior to the rise of human populations. In
some coastal areas, the flux of nutrients via groundwater seepage is of
the same order of magnitude as that delivered by fluvial runoff
(Rutkowski et al., 1999), the higher concentrations of nutrients
compensating for the lower flow rates compared with riverine flows.
Although groundwater inputs may contribute significantly to primary
productivity in some local areas (Burnett et al., 2003; Slomp and Van
Cappellen, 2004), reliable estimates of this nutrient source to the ocean
on a global scale are very limited because groundwater flow into the
ocean is diffuse and patchy.
2.4.3. Atmospheric nutrient source
An atmospheric supply of fixed-N to estuaries and the coastal
ocean has increased markedly over the last several decades, again as a
consequence of industrial and agricultural activities (Paerl, 1993,
1995). Although the impact of this source is currently important in
areas downwind of major population centers, it was not important
compared with natural sources prior to the anthropogenic era.
2.4.4. Oceanic nutrient sources
The impacts of fluvial, groundwater, and atmospheric sources of
nutrients to the ocean pale in comparison to the supply of nutrients to
surface waters from the ocean interior. Waters deeper than the surface
mixed photic layer of the ocean have higher concentrations of nu-
trients than surface waters. More than 90% of the nutrients extracted
from the photic zone by an opportunistic biological community are
returned to solution at depth by microbial remineralization (Fig. 4).
They are then returned to the photic zone by advection, vertical
mixing, and diffusion. This biological pump (McElroy, 1983; Knox and
McElroy, 1984) maintains the concentration gradient between surface
and deep waters (Sarmiento and Gruber, 2006), opposing the
tendency for the uniform distribution of nutrients in ocean waters
by advection and mixing.
At high latitudes, surface- and deep-water nutrient levels are
homogenized during winter months when production is light limited.
Warming in spring, which stabilizes surface waters, sets the condi-
tions for the spring algal bloom when there is sufficient light for
photosynthesis (Mann and Lazier, 2006). At lower latitudes, surface
waters are re-fertilized by mixing across the pycnocline (diapycnal
mixing) and by the upward flow of waters from below the
thermocline, a process known as upwelling (Sverdrup et al., 1942).
Upwelling is prevalent along continental margins that experience
across-shelf transport of surface water and in the open ocean along
the equator.
Upwelling is driven by divergence of surface waters (equatorial
case; Sverdrup et al., 1942) and by transport of surface waters away
from a coastline (Wyrtki, 1962; Smith, 1995), expressions of Ekman
transport. Continuity requires the transport of surface water to be
compensated by the upwelling of sub-surface water, with its higher
nutrient content than the surface water it replaces (Fig. 4). Upwelling
occurs at the equator in the Pacific Ocean due to the change in the
Coriolis deflection as the Trade Winds reach across the geographical
equator (the meteorological and geographical equators do not
coincide), and between juxtaposed surface currents flowing in
opposite directions north of the equator (Sverdrup et al., 1942).
71
Upwelling of sub-surface water also takes place in the Antarctic
Circumpolar Current with the transport of surface waters away from
the continental boundary due to the westerly winds (Gordon, 1971).
Upwelled water along coastlines and the equator is drawn to the
surface from depths not exceeding 200 to 300 m (Sverdrup et al.,
1942) and, in some cases, shallower than 100 m depth (Codispoti,
1980). In spite of the shallow source, this upwelled water has a higher
nutrient content than surface water, although not as high as abyssal
waters (Fig. 4). The moderately higher contents result from the first
stages of the remineralization of labile organic matter settling to depth
from the surface productive layer of the sea and by lateral transport
from the Southern Ocean. The vertical flow, or upwelling, of this water
then serves to replenish the surface layers with regenerated nutrients
(Chavez and Smith, 1995; Hutchings et al., 1995).
Nutrient inventories in shallow sub-surface waters of the ocean
vary on climatic timescales that are controlled by the mode of
circulation of the ocean's deep overturning circulation (Toggweiler
et al., 2006). Around Antarctica, the eastward flowing surface
circulation diverges northwards away from the continent, inducing
large-scale upwelling of deep water. The upwelled water is relatively
nutrient-enriched because it is derived from the southern branch of
the deep overturning circulation where regenerated nutrients from
the entire Atlantic have accumulated during the southward flow of
deep water. The upwelled water now at the surface is driven
northwards by Ekman transport. After surface cooling and vertical
convective homogenization during the winter, it sinks to shallow
intermediate depths as the Subantarctic Mode Water (McCartney,
1977) and circulates through the thermoclines of all ocean basins as
Antarctic Intermediate Water. This supply of sub-thermocline waters
to all ocean basins delivers nutrients that ultimately drive low-latitude
primary production (Sarmiento et al., 2004).
Nutrient supply by this mechanism probably changed on glacial–
interglacial timescales due to changes in ocean stratification and/or
changes in Southern Ocean upwelling. Glacial deep ocean waters were
denser than modern abyssal waters because of intense sea ice
formation near Antarctica. This slowed vertical mixing and conse-
quently reduced upwelling (Watson and Naveira Garabato, 2006).
Upwelling could also have been reduced by the weakening and
northward migration by 7°–10° latitude of the circum-Antarctic wind
belt (Toggweiler et al., 2006). This would have suppressed upwelling
of deep water near Antarctica leading to decreased nutrient re-supply
to thermocline waters. As thermocline depths are the source regions
for coastal and equatorial upwelling, nutrient supply to surface waters
and hence productivity would have been modulated by glacial events.
Plankton nutrition prior to the Pleistocene could also have been
affected on other time scales, e.g., long-period changes in sea level
(Haq et al., 1987; Miller et al., 2005) that resulted in flooding events on
continental margins and changes in atmospheric temperatures
(Scotese, 2001).
Although the ultimate sources of all nutrients to ocean waters are
the atmosphere and continents, the proximate nutrient supply to
surface waters is dominantly from within the ocean itself, namely
relatively shallow sub-surface waters, whence nutrients are entrained
into the photic zone by mixing and by upwelling. A recent modeling
study of nutrient supply to surface waters of the North Atlantic
(Oschlies, 2002) has shown that vertical mixing is the dominant
supply mechanism in the subpolar region, while upwelling is most
important in equatorial and coastal regions. Upwelling alone, in the
coastal, equatorial, subpolar, and monsoonal systems, accounts for
around three quarters of the new production in the ocean (Eppley and
Peterson, 1979), that production fueled by nutrient supply from
outside the surface layer (Chavez and Toggweiler, 1995). These two
source vectors, together with the low-intensity diapycnal mixing
across the strong thermocline in the central subtropical gyres, sustain
almost all “new” production in the ocean as a whole, dwarfing local
supplies from the atmosphere, rivers, and ground waters.
72 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
2.5. Trace-element sources
The sources of trace elements to the oceans are (1) the weathering
and erosion of the continents, which supply trace elements to rivers
and the atmosphere (Rex and Goldberg, 1958; Martin and Meybeck,
1979), and (2) submarine hydrothermal activity, largely in the deep
ocean (Lyle, 1976; Corliss et al., 1979; Von Damm, 1990). For most
trace elements, their transit time in and mixing rates of the ocean
preclude identification of local sources. Trace elements in marine
deposits can therefore be viewed as having either a lithogenous
source or a seawater source (Goldberg, 1963). Marine sources include
seawater, whereby trace elements are removed from the water
column as precipitates and adsorbed phases and/or by diffusion
across the benthic boundary (hydrogenous fraction), and particulate
organic matter that settles onto the seafloor mostly from the photic
zone, having escaped oxidation in the water column (biogenous
fraction).
Advances in our understanding of the thermodynamic properties
of seawater, trace metals, and marine mineral phases (Sillén, 1961;
Garrels and Christ, 1965, Stumm and Morgan, 1996; Millero, 2001)
made since the middle of the last century have provided the means to
hindcast depositional conditions in the rock record. Insight into the
factors leading to individual element enrichments and depletions in a
given sedimentary deposit was further improved through the rapid
development within the past 45 years of new analytical techniques for
determining trace element and organic matter concentrations in
seawater and modern marine sediments from a wide spectrum of
depositional environments (e.g., Brewer and Spencer, 1974; Boyle
et al., 1976, 1977; Bacon et al., 1980; Elderfield and Greaves, 1982;
Jacobs and Emerson, 1982; Bruland, 1983; Kremling, 1983; Jacobs et al.,
1985, 1987; DeBaar et al., 1988; Emerson and Huested, 1991; Landing
and Lewis, 1991; Piper and Wandless, 1992; German et al., 1993;
Sholkovitz, 1993; Crusius et al., 1996; Calvert et al., 2001; Hedges et al.,
2001). A major result of this work has been the precise analysis of
those trace elements whose accumulation in marine sediments and
sedimentary rocks is diagnostic (Fig. 3) of deposition under oxic (Mn
and Fe), suboxic (Cr, Re, U, and V), and fully anoxic bottom-water
conditions (Mo, Cd, Cu, Zn). Similarly, knowledge of the marine
biogeochemical cycling of trace nutrients by plankton (Fig. 4), e.g., Ba,
Cd, Cu, Ni, and Zn (Martin and Knauer, 1973; Collier and Edmond,
1983; Brumsack, 1986; Whitfield, 2001; Ho et al., 2003) has
contributed to an improved insight into the role of primary produc-
tivity in cycling trace nutrients through the ocean and their eventual
accumulation on the seafloor.
2.5.1. Lithogenous trace-element source
The contribution of major and trace elements to a deposit by the
lithogenous source, largely siliciclastic debris, can be modeled from
bulk-sediment analyses (Leinen, 1977; Calvert and Price, 1983; Piper
and Isaacs, 1994, 1996), or by chemical extractions (Chester and
Hughes, 1967; Tessier et al., 1979). In the modeling approach, the
lithogenous contribution of an element is determined by normalizing
its concentration to a major-element oxide that is hosted solely in the
siliciclastic sediment fraction (Calvert and Pedersen, 2007). Alumina
(Al2O3) is frequently used for this purpose as it constitutes one of the
essential building blocks of aluminosilicate mineral phases and its
concentration is similar in acidic to basic extrusive and intrusive
igneous rocks, most metamorphic rocks, the bulk upper crust, and
shales (Wedepohl, 1971; Taylor and McLennan, 1985; Wedepohl,
1995). However, the total composition of the different standards of
siliciclastic debris varies considerably, reflecting both real and
procedural differences (Wedepohl, 1995). For example, titanium has
been used in a similar way to (Al2O3), but its content varies more
widely in different rock types, and it can be enriched in coarse-grained
fractions of sediments during deposition as it occurs in Ti-rich heavy
minerals (Spears and Kanaris-Sotiriou, 1976).
We use a slightly different procedure to establish the composition
of this fraction in any sedimentary deposit than taking the
composition of a single standard as the model composition of the
lithogenous fraction, although the standards provide a check on the
final model composition. Trace-element and major-element-oxide
ratios used to evaluate the composition of the lithogenous fraction
include K2O:Al2O3, Th:Al2O3, Rb:Al2O3, Co:Al2O3, and Ga:Al2O3. All of
these major and trace elements have a dominantly lithogenous
siliciclastic source, thus the constancy of such ratios in a series of
sediments or rock samples provides support for the use of a single
composition for this fraction. The similarity of the ratios to that of a
single standard, such as a World Shale Average (WSA) and
continental crust (CC) (Turekian and Wedepohl, 1961; Wedepohl
et al., 1969–1978; Wedepohl, 1971), upper continental crust (UCC)
(Taylor and McLennan, 1985; Wedepohl, 1995), post-Archean
Average Shale (PAAS) (Taylor and McLennan, 1985), or North
American Shale Composite (NASC) (Gromet et al., 1984; Condie,
1992) further supports the selection of a single composition for this
sediment fraction (Piper and Isaacs, 1994, 1996; Piper and Dean,
2002; Piper et al., 2007; Perkins et al., 2008) in any single deposit.
The lithogenous contribution of elements that may be enriched
above their concentration in the lithogenous source-rock model is also
determined by normalizing bulk concentrations to Al2O3 (Piper and
Isaacs, 1996; Perkins et al., 2008; Calvert and Pedersen, 2007). On a
plot of element versus Al2O3, a curve drawn from the origin through
samples with the lowest concentration of the element in question
establishes the element:Al2O3 ratio of the lithogenous model. This
value, or the slope of the curve, is again compared to element:Al2O3
ratios of the shale standards. In the case of the KCF, the slopes of these
minimum curves for Ni, V, and Mo versus Al2O3 are within 10% of their
ratios in the WSA (Fig. 5), well within the variations in composition
between the different shale standards. Copper and Zn have slopes that
are roughly two-thirds their respective ratios in the WSA, but close to
mean ratios in the UC and CC standards (Wedepohl, 1995). The con-
centration of Al2O3 in a sample, together with the element:Al2O3 ratio,
provides an estimate of the lithogenous contribution of the element
itself.
The relationship between Hf and Zr, both of which have a solely
lithogenous source, serves several purposes in evaluating the nor-
mative scheme. The strong correlation between these two elements
(Fig. 6) reflects their close chemical similarity (Hampel, 1968) and,
thus the quality of the analyses and the constancy of composition
of the lithogenous fraction in any single deposit. The slightly different
Hf:Zr ratios in various “standards”, however, demonstrate the
problem of relying on the composition of a single sedimentary rock
standard as the model composition for the lithogenous fraction of all
deposits.
The alternative method of identifying the lithogenous fraction is by
separating operationally defined fractions of a sediment sample by
chemical leaching methods (Chester and Hughes, 1967; Tessier et al.,
1979). One aim is to leave the lithogenous material relatively
unaffected, thus isolating the soluble fraction(s) that may represent
the marine fraction of a trace element from the lithogenous con-
tribution. Incomplete extraction of a given component or the simul-
taneous extraction of portions of two or more fractions, depending on
the choice of extracting reagents, can bias these results (Sholkovitz,
1989; Nirel and Morel, 1990; Tessier and Campbell, 1991). The success
of this procedure in isolating the marine fraction can be evaluated by
an analysis of the insoluble fraction and its similarity in composition,
again, to a shale standard (Piper and Wandless, 1992). Both methods
have their obvious limitations.
2.5.2. Seawater trace-element sources, trace nutrients and redox-sensitive
trace metals
In the modeling scheme, trace-element concentrations that plot
above the trace element versus Al2O3 minimum curves in x–y plots
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 73

Fig. 5. Relationship between Al2O3 and selected trace elements, Fe2O3, and Corg in the KCF. The Th:Al2O3 ratio in samples from all sections except OPI-2/1 is close to that of the world
shale average, or WSA (Gromet et al., 1984), and the single trend extrapolates to the origin. We can offer no explanation for the seemingly high Al2O3 (low Th) values in OPI-2/1. The
Fe2O3 values in all units except OPI 2 scatter above and below the curve for the WSA, suggesting a lack of Fe enrichment, on average. The trace elements other than Th and Fe2O3 are
uniformly enriched above a lithogenous contribution, represented by their displacement above a curve drawn through the samples with the lowest trace-element:Al2O3 ratios. The
slopes of these minimum curves in frames D–H closely approach trace-element:Al2O3 ratios for the different trace elements in the WSA, shown by asterisks. The displacement of
samples above the curves in these frames is taken as the seawater-derived marine fraction of trace elements (see text). The relationships between Al2O3 and Corg (frame C) in samples
of the separate units within the Cleveland Basin exhibit negative trends with the omission of a single analysis from OPI-1. Correlation coefficients and p values of the linear
regressions for the different units are shown in the legend in parentheses. Samples from the Boulonnais Basin site exhibit a positive trend, but the correlation is weak and the p value
is large. Nonetheless, the samples are distinct from those of units from the Cleveland Basin. The shaded areas in frames F and G enclose samples from Argiles de Chatillon.
74 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96

Westerlund, 1988, 1991), its rate of deposition can be used to estimate

Fig. 6. Relationship between Hf and Zr in samples from the Boulonnais Basin site in
northern France. Their ratio is similar to the mean for WSA, the North American Shale
Composite (NASC), the upper continental crust (UC), and the lower continental crust
(CC). Data for the standards are from Wedepohl et al. (1969–1978), Gromet et al.
(1984), and Wedepohl (1995).
(Fig. 5) identify the marine fraction of trace elements (Piper et al.,
2007) that are contributed by biogenous debris (biogenous fraction)
and precipitates and adsorbed phases (hydrogenous fraction) on a
sample-by-sample basis. Concentrations of individual trace elements
and inter-element ratios within the marine fraction alone may
identify relative levels of primary productivity and bottom-water
redox conditions. As an example, the Ni:Al2O3 ratio in the bulk
sediment identifies the marine input of Ni to the seafloor of an anoxic
basin (Piper and Dean, 2002). From our understanding of its
geochemistry in seawater (Jacobs et al., 1985, 1987; Haraldsson and
the flux of Corg settling out of the photic zone. This interpretation is
based on the observation that Ni is intimately involved in biogeo-
chemical cycling in the ocean, for which its mean concentration
measured in plankton of ca. 18 ppm (Collier and Edmond, 1983) is in
close agreement with the value calculated (Piper and Dean, 2002)
from its depth profile in the ocean (Sclater et al., 1976; Whitfield,
2001; Cotté-Krief et al., 2002; Fig. 4). The Ni:P ratio measured in
organic matter is 2.1 × 10− 3 g g− 1, whereas the ratio obtained from
the increase in the concentration of dissolved Ni and P from the photic
zone to below the main pycnocline in the Pacific Ocean, in response to
remineralization of organic matter, is 2.7 × 10− 3 g g− 1. In the North
Atlantic, the profiles of Ni and HPO2− 4 in the upper ca. 500 m of the
water column yield a ratio that is close to 2 × 10− 3 g g− 1 (Cotté-Krief
et al., 2002). By contrast, both the addition of Ni to the O2-depleted
part of the water column of anoxic basins (e.g., Saanich Inlet,
Framvaren Fjord, the Cariaco Basin (Fig. 7) and the Black Sea) via
remineralization of organic matter and its removal by inorganic
processes appear to be insignificant (Jacobs et al., 1985, 1987; François,
1988; Haraldsson and Westerlund, 1991) because its concentration is
uniform with depth. Thus, the accumulation of the seawater-derived
fraction of Ni in sediments that accumulate under O2 depleted
bottom-water conditions provides an indirect estimate of Corg settling
out of the photic zone and its deposition on the seafloor prior to burial
and post-depositional oxidation of the deposited organic matter.
In contrast to the behavior of Ni, the biogenous contribution of Mo
and V to sediments is minor. Concentrations in phytoplankton average
less than 2 to 3 ppm (Brumsack, 1986) and their dissolved con-
centrations exhibit minor enrichments with depth below the photic
zone (Fig. 4). Vanadium is reduced to the strongly adsorbed VO(OH)− 3
under moderate suboxic conditions (Emerson and Huested, 1991).
Conversely, high dissolved sulfide concentrations are required to

Fig. 7. Depth profiles of selected trace elements and nutrients in the Cariaco Basin. The profiles are similar in other anoxic basins, but absolute concentrations vary slightly. For
example, Mo in the Black Sea has its highest concentration of ca. 75 nmol L− 1 in the very surface water and decreases more or less uniformly to ca. 5 nmol L− 1 at 300 m depth, below
which it maintains a uniformly low concentration (Emerson and Huested, 1991). The particulate Mn maximum in the Black Sea is also in the suboxic zone but at a much shallower
depth; otherwise, its profile and that of dissolved Mn (Brewer and Spencer, 1974) are virtually the same as in the Cariaco Basin. The Fe profiles in the two basins also are similar. In the
Cariaco Basin, the particulate Fe distribution is complicated by a high lithogenous contribution (Bacon et al., 1980), particularly in the near-surface water. The data for Mo and V are
from Emerson and Huested (1991); data for Cd, Ni, dissolved Fe, and dissolved Mn are from Jacobs et al. (1987); the data for particulate Mn, HPO2− 4 , and H4SiO4 are from Richards
(1975). The particulate Fe curve represents a combining of data from Richards (1975) and Bacon et al. (1980). The Ni curve represents a three-floating-point average. The Ni data of
Haraldsson and Westerlund (1988) for the Black Sea show that it is not significantly depleted in the deep water, similar to its distribution shown here for the Cariaco Basin. By
contrast, Landing and Lewis (1991) report a 40% lowering of Ni in the bottom water of the Black Sea. Profiles of fixed-N in both basins are similar to those shown in Fig. 3. The color
coding is given in Fig. 3. As chemical interfaces migrate as much as 100 m seasonally (Thunell, personal communication, 2007), some adjustment of sample depths has been
attempted based on the depth of the suboxic–anoxic interface.
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
initiate efficient conversion of soluble molybdate to thiomolybdate
species, which are then fixed as S complexes (Helz et al., 1996). These
reactions lead to the removal of V and Mo from O2-depleted seawater
(Emerson and Huested, 1991) and accumulation in sea-floor sedi-
ments under slightly different bottom-water redox conditions, V
under suboxic and anoxic bottom-water conditions and Mo only
under fully anoxic conditions. The V:Mo ratio in the marine-sediment
fraction will then distinguish between these two redox conditions
of bottom waters (Piper and Isaacs, 1994, 1996; Piper et al., 2007).
Under fully anoxic conditions, the V:Mo ratio in the sediment should
approach its ratio in seawater itself, ca. 1.8:10. The weak biogenous
signal of both metals and their different efficiencies of removal from
anoxic seawaters (Emerson and Huested, 1991; Piper and Dean, 2002)
will change this ratio in the sediment slightly, but should not increase
it significantly above ca. 2. Under suboxic bottom waters, i.e., where
SO2−4 reduction is restricted to the sediment pore water, V:Mo ratios in
the sediment will be elevated above their seawater ratios. Sediments
that accumulated under bottom-water conditions that varied through
time from suboxic to anoxic should also exhibit elevated marine V:Mo
ratios. A sampling scheme for studying sedimentary rocks, for which a
centimeter section can represent as much as several hundred years,
imposes on an individual sample the probability that it may have
recorded multiple conditions of bottom-water redox. Conversely, an
extended sediment section that exhibits a strongly uniform V:Mo ratio
would be indicative of a stable water column. Crusius et al. (1996)
showed that the accumulation rates of Re and U driven by their
diffusion across the benthic boundary (Anderson et al., 1989) have a
relationship with Mo in sediments that is similar to the observed V
and Mo relationship in the sediments.
Tribovillard et al. (2008) have cautioned against the use of Mo
enrichment as a proxy for bottom-water anoxia in ancient sediments
in the absence of enrichments of other redox-sensitive trace elements,
e.g., Re, U, and V. They note that Mo may be taken up by framboidal
pyrite during early diagenesis under oxic to suboxic bottom-water
conditions. This mechanism of Mo enrichment may result in an over-
estimation of the importance of Mo enrichment as solely indicative of
anoxic bottom-water conditions. Zheng et al. (2000) and McManus
et al. (2006) have further reported Mo accumulation under less than
anoxic conditions. Thus, bottom waters may have been less reducing,
i.e., suboxic, when Mo concentrations alone indicate the bottom water
was anoxic. In such sedimentary rocks, framboidal pyrite should be an
important component of the sediment and host of Mo that had a
seawater source (Tribovillard et al., 2008).
2.5.3. Trace-element accumulation rates
Although the trace-element ratios discussed here identify bottom-
water redox conditions of deposition, they do not provide information
on rates of hydrographic, biological, and chemical processes that
contribute to an understanding of the dynamics of the sedimentary
environment e.g. rates of nutrient and trace-element supply to a basin,
primary productivity, upwelling, and advection of bottom water and
its residence time (RT) in a basin. The accumulation rates of individual
trace elements alone allow these aspects of deposition to be addressed
and for that sediment accumulation rates are required. Bulk-sediment
accumulation rates can be estimated by assuming that the linear
thickness of a sedimentary section between two horizons of known
age represents the flux of sedimentary material settling through the
water column during that time interval (Eq. (1)), as opposed to the
lateral transport of sediment. The accumulation rates of individual
trace elements then provide insight into (1) the level of organic
production from the accumulation rate of trace nutrients and (2) the
hydrography, or the circulation and the oxygenation of the waters
from the accumulation rates of redox-sensitive trace metals.
Linear sedimentation rates are commonly assumed in calculations
of trace-element fluxes to the seafloor. Important caveats to the
modeling procedure employing sedimentation rates from linear
75
section thicknesses between dated horizons are the presence of
laterally supplied sediment in the sedimentary section (focusing) and,
conversely, the removal of material by sea-floor erosion (winnowing).
These problems have been highlighted in Late Quaternary sediments
of the mid-latitude Atlantic (François et al., 1990), the Southern
Ocean (Frank et al., 1995), and the equatorial Pacific (Marcantonio
et al., 2001; Loubere et al., 2004; Anderson et al., 2006; Kienast et al.,
2007). For Holocene and Late Pleistocene sediments, corrections for
these effects have been developed using the 230Th-normalization
technique (François et al., 2004). Because of the short half-life of
230
Th, this approach is only applicable for sediments younger than
ca. 350,000 years.
2.5.4. Limitations of modeling trace-element ratios and accumulation rates
Estimates of the concentrations of trace elements in the two
marine fractions of sediment become problematic (1) when the
marine contribution of an individual trace element approaches the
uncertainty of the analytical technique and (2) when the composition
of the lithogenous fraction of the sediment, represented by the slopes
of trace elements versus Al2O3 plots (Fig. 5), fails to identify a single
composition that is similar to the various rock standards. In the case
considered here, the adoption of a single composition for this fraction
in the KCF is supported by the close similarity of the slopes of the trace
element versus Al2O3 curves to their ratios in the crustal standards.
The use of bulk-sediment concentrations and concentration ratios,
without adjusting for contributions by siliciclastic components,
severely compromises the modeling of elemental fluxes. This ap-
proach limits the sensitivity and accuracy of identifying and inter-
preting the marine sources of diagnostic elements. For example, the
bulk-sediment V:Mo ratio of the Black Sea surface sediment is 7
(Volkov and Fomina, 1974; Calvert, 1990), largely reflecting the much
higher V concentration in lithogenous siliciclastic detritus (100 to
150 ppm) than Mo (2 to 3 ppm). Given the seawater concentrations of
V (1.8 ppb) and Mo (10 ppb) and the efficiency of their removal from
the Black Sea anoxic waters of 75% and 95%, respectively (Emerson
and Huested, 1991), their seawater-derived V:Mo ratio is unlikely to
be greater than one. The ratio of their marine fractions in surface
sediment from the Black Sea is indeed less than 1.5 (see Section 3.2.4).
The V:Mo ratio in surface sediment from the Cariaco Basin is 0.65
(Piper and Dean, 2002). A significantly higher ratio in the marine
fraction of a number of sedimentary deposits, e.g., the Quaternary
sediment from the Japan Sea (Piper and Isaacs, 1996), the Miocene
Monterey Formation of California (Piper and Isaacs, 1994), the Permian
Phosphoria Formation of the northwest United States (Piper, 2001),
and the Devonian Ohio Black Shale of the eastern United States
(Perkins et al., 2008), must reflect deposition under dominantly
suboxic conditions.
The bulk Ni:Co ratio, which has been used to identify anoxic water-
column conditions (Jones and Manning, 1994; Rimmer et al., 2004),
has even more severe limitations for deducing the redox status of
sediments. Nickel has both a lithogenous and a biogenous source,
whereas Co has primarily a lithogenous source (Brewer and Spencer,
1974; Jacobs et al., 1985, 1987). Therefore, the uncorrected bulk-
sediment ratio provides no information about bottom-water anoxia
and less precise information about the possible enrichment of Ni by
the biogenous fraction than given by the Ni:Al2O3 ratio. We should add
that Co does have a hydrogenous source under oxic conditions (see
Section 3.2).
The V/(V + Ni) ratio, or some variant of the ratio, in bulk sediment
has also been used to identify anoxic conditions in the geologic record.
Enrichments of both metals were ascribed by Lewan and Maynard
(1982) to the metallation of porphyrins, which are themselves
enriched in fine-grained shallow-water sediments that have anoxic
sediment pore waters, but were not necessarily deposited from anoxic
bottom waters. Thus, the use of the bulk-sediment V/(V + Ni) ratio to
identify anoxic bottom-water conditions of sedimentation, as opposed
76 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
to sediment pore waters, is an inappropriate extension of the findings
of Lewan and Maynard (1982).
These results show that the estimate of the strictly marine
contributions of trace metals to a given deposit yields a much more
reliable reconstruction of past geochemical properties of marine
waters, and that bulk-sediment compositions and ratios are less
informative in this respect.
3. Modern marine environments
Studies of the geochemistry of the sediments in several modern
anoxic marine basins have provided insight into the accumulation of
those trace elements that behave as proxies for the delivery of
biogenic materials to the basin floor (biogenous sediment fraction),
as proxies of water-column redox (hydrogenous sediment fraction),
and as proxies of the relatively non-reactive siliciclastic sediment
(lithogenous sediment fraction). The rate of accumulation of the
biogenous fraction reflects rates of nutrient supply to the photic zone,
i.e., primary productivity, by upwelling and/or mixing, whereas the
rate of accumulation of the hydrogenous fraction tracks changes in
bottom-water advection and redox. The rate of accumulation of the
lithogenous fraction provides an estimate of the dilution of the
marine fractions by terrigenous debris. We review some of the results
of studies of two anoxic basins—the Cariaco Basin and the Black Sea—
to illustrate the processes that govern sediment compositions in
these two environments. The calculations that follow provide a
quantitative illustration of trace-element accumulation rates on the
seafloor of these two basins that are consistent with their different
hydrographies and water-column geochemistries. The results then
serve as a guide for our interpretation of the environment of
deposition of the KCF.
The seafloor in the Cariaco Basin and Black Sea reach depths of
1400 m and 2200 m, respectively; sill depths are 140 m and 40 m,
respectively. Water-column redox profiles in the two are similar
(Fig. 3). They have a surface mixed, oxic layer several tens of meters
thick. In the Black Sea, the thickness of the surface layer has decreased
in recent years, owing to anthropogenic inputs of nutrients (Polat and
Tuğrul, 1995, and references in Özsoy and Ünlüata, 1997). Both basins
have an intermediate suboxic layer, in which bacterial respiration
lowers the concentration of fixed-N to zero. In the Black Sea, the
suboxic layer is only about 25 to 75 m thick, whereas it is as much as
150 m in the Cariaco Basin (Thunell et al., 2000; Goñi et al., 2003). The
bottom water in both basins is sulfidic.
The basins are useful modern analogues for ancient black shales,
although we do not imply by this that barred basins are the favored
paleobathymetric model for basins in which black shales have
accumulated. Sediment texture of both deposits reflects the partial
isolation from the ocean that renders their sea-floor environments
tranquil. Their sediments are fine-grained and finely laminated. Laminae
in sediment recovered from a 900 m deep saddle in the Cariaco Basin,
which separates two 1400 m deep sub-basins, represent annual varves
(Hughen et al., 1996). The sediment texture of the KCF (Wignall, 1990)
and of other black shales in the geologic record is also commonly
laminated, suggesting low-energy bottom-water conditions.
This property contrasts sharply with environments on open
continental shelves, where oxygen-depleted seawater in the OMZ
intersects the shelf at depths between roughly 100 and 800 m,
(Wyrtki, 1962, 1963; Codispoti, 1980, 1989; Kuypers et al., 2005). For
example, sediments on the Peru shelf show strong textural and
geochemical evidence of suspension and redeposition by the under-
current beneath the Peru Current (Kim and Burnett, 1988; Arthur and
Dean, in press) that sweeps over the shelf. This property is a
prominent feature of other open ocean, continental shelf deposits
that exhibit high primary productivity (van Andel and Calvert, 1971;
Arthur et al., 1998), in marked contrast to the texture of sediments
accumulating in the tranquil environment of silled basins. The shelf
environments are further distinguished by being more or less per-
manently suboxic, seldom anoxic (Dugdale et al., 1977). As discussed
previously, the seafloor beneath some OMZs can be densely inhabited
by macrofauna, owing to a large flux of O2 over the seafloor delivered
by a strong bottom current, despite having near zero O2 concentration
(Arthur et al., 1998).
An exception to this generalization occurs within the OMZ
between 200 and 800 m depth in the Gulf of California and off
northwestern Mexican (Calvert, 1964; Ganeshram and Pedersen,
1998). Finely laminated sediment is currently accumulating on these
continental slopes under suboxic conditions. Similar to a true basin
setting, the gulfs are partially separated from the open ocean. In the
case of the Gulf of California, it is isolated from the California Current,
the eastern boundary current of the Northeast Pacific Ocean, but it is
without a sill that would otherwise limit water exchange with the
Pacific. A second possible analogue is the inner shelf off Namibia,
where organic-rich, highly sulfidic diatomaceous muds are currently
accumulating on a 100 m deep platform beneath the highly
productive Benguela Current (Calvert and Price, 1983). Bottom
waters here are seasonally suboxic due to the high settling flux of
planktonic debris (Calvert and Price, 1971; Bailey, 1991; Tyrrell and
Lucas, 2002). Occasional fish kills (Copenhagen, 1953) are caused by
the intermittent presence of dissolved sulfide in the waters (Brüchert
et al., 2003). In this view, a black shale basin may not necessarily
have been a bathymetric feature, but a site of deposition where
bottom circulation was restricted by shelf breadth and only partially
isolated from the open ocean. This usage follows that developed from
the extensive work on the modern sedimentary environments of the
Gulf of Mexico and the Gulf of California (Shepard et al., 1960; van
Andel and Shor, 1964). A basin, or shelf depth less than ca. 300–
400 m, would further allow the most intensely negative redox
conditions to occur at the seafloor rather than at an intermediate
depth of an OMZ.
The extrapolation of relationships between the marine chemistry
and hydrography of modern basins to those properties of ancient basins,
based on trace-element accumulation rates, are certainly limited by
uncertainties related to variations through time of: (1) the trace-
element geochemistry in seawater (Algeo, 2004): (2) the uptake of trace
nutrients by plankton (Quigg et al., 2003): (3) diagenesis of sediments
following deposition and burial: (4) weathering following uplift and
exposure: and (5) uncertainties in estimates of the trace-element
marine faction of sediment using a single model for the lithogenous
fraction. For these reasons, the following calculations that elucidate the
oceanographic dynamics of modern basins in the short term can only be
applied to time-averaged conditions of an ancient basin.
3.1. The Cariaco Basin
The Cariaco Basin is a relatively small depression on the con-
tinental shelf of Venezuela, consisting of two 1400 m-deep sub-basins
separated by a 900 m deep saddle. It is partially isolated from the
Caribbean by a 145 m deep sill. During the last glacial maximum
(LGM), the basin was nearly isolated from the Caribbean Sea. A rising
sea level, beginning about 18 ka (Fairbanks, 1989), imposed a complex
signal of temporal changes on rates of upwelling, bottom-water
advection, and the flux and composition of lithogenous debris into the
basin (Peterson et al., 1991; Yarincik et al., 2000). These changes are
now reflected in the lithology of the sediment. In a piston core from
the 900 m deep saddle (Peterson et al., 1991, 1995), the sediment is
bioturbated below approximately 600 cmbsf (centimeters below the
seafloor). It is distinctly laminated above this unit to about 300 cmbsf,
and less distinctly and more thinly laminated from 300 cmbsf to the
sediment surface. The laminae consist of alternating biogenous
(carbonate and/or diatomaceous silica) and clay-rich layers, each
lamina couplet representing an annual varve (Hughen et al., 1998).
Peterson et al. (1991) interpreted the lithologic boundary between the
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 77

bioturbated and the laminated units, dated at 14.8 ka (Lin et al., 1997; equivalent to oxidation of the Corg, is given by their reduction in the
Hughen et al., 1998), as recording the onset of elevated primary lowermost 1100 m of the water column:
productivity in the photic zone and of SO2−4 reducing conditions in the
bottom water. These properties of the water column continue to the Oxic respiration : 10CH2 O + 10O2 + 10CaCO3 = 20HCO3− + 10Ca2 +
present (Richards, 1975). Corg oxidation = reduction of oxidantðsÞ
Partial isolation of the Cariaco Basin and a high settling flux of Corg
to depth (Thunell et al., 2000; Goñi et al., 2003) maintain anoxic ½
= 0:185 mol O2 m
−3
× 0:4 × 1100 m
conditions in the bottom water. Oxygen concentrations decrease from 
× 1:0 mol Corg mol − 1 O2 = 82 mol Corg m − 2 :
a maximum of ca. 210 µM in near-surface waters (Fig. 3) to zero at ca. ð3Þ
300 to 350 m depth (Richards, 1975; Scranton et al., 2001), where H2S
increases with depth, reaching a concentration of ca. 40 µM in the Suboxic respiration : 10CH2 O + 8NO3− + 2CaCO3
abyssal waters (Fanning and Pilson, 1972; Emerson and Huested, 1991; − 2 +
= 12HCO3 + 4N2 + 4H2 O + 2Ca Corg oxidation
Scranton et al., 2001). The water column at intermediate depth (150 to h

− −3
= 0:005 mol NO3 m × 0:70
300 m) is suboxic, or denitrifying. Fixed-N, mostly as NO− 3 , generally is


very low in the near-surface waters, but increases to ca. 12 µM at
200 m due to nitrification. Below this depth, it decreases to zero at 300
× 1100 m × 1:25 mol Corg mol − 1 NO3− 
to 350 m. The other important forms of fixed-N (NH+ −
= 5 mol Corg m − 2 : ð4Þ
4 and NO2 ) are
also forced to zero at this same depth (Fig. 3) by anammox reactions
(Schmidt et al., 2002; Dalsgaard et al., 2003; Kuypers et al., 2003,
Anoxic respiration : 10CH2 O + 5SO24 − + 5CaCO3
2005), by some variant of the following reaction:
= 15HCO3− + 5HS − + 5Ca2 + Corg oxidation
h

i
þ − −
3:33NH4 + 2NO2 + 0:66HCO3 + 0:33CaCO3 = 0:040 cmol SO24 − m − 3 ×1100m × 2 mol Corg mol − 1 SO24 −

= 2:66N2 + CH2 O + 0:33Ca

2 +
+ 6H2 O: ð2Þ = 88 mol Corg m − 2 : ð5Þ

Below this depth ammonium concentrations increase, reaching
ca. 15 µM in the deep waters. Phosphate and silicic acid are also in low
concentration in the near-surface waters (Fig. 7), but increase
smoothly with depth below the pycnocline to maximum values in
the abyssal waters of 3 and 70 µM, respectively (Fanning and Pilson,
1972; Richards, 1975).
Primary productivity is highly seasonal but averages 550 g Corg
m− 2 yr− 1 (Varela et al., 1997; Goñi et al., 2003). It is supported by
the input of nutrients in sub-thermocline waters from the Caribbean
Sea (Richards, 1975). Goñi et al. (2003), Müller-Karger et al. (2001),
and Thunell et al. (2000) have shown that primary productivity is
highest between December and April, when the Intertropical
Convergence Zone (ITCZ) lies south of the equator and the strong
northeasterly trade winds create intense upwelling along the coast-
line. Water entering from the Caribbean across the sill at approxi-
mately 100 to 200 m depth (Müller-Karger et al., 2001) upwells into
the photic zone when the near-surface thermocline is weakly
developed and the 22 °C isotherm penetrates to the surface. During
the summer and fall a strong thermocline develops at 50 m and
upwelling and primary productivity are depressed.
3.1.1. Oxidant balance in and residence time of bottom water
The mean flux of Corg settling into the anoxic bottom water is
1.92 mol m− 2 yr− 1 (Thunell et al., 2000; Goñi et al., 2003); 30% is
buried on the seafloor and 70% is oxidized in the water column and at
the benthic boundary. As essentially all of the Corg has a marine origin
(Wakeham and Ertel, 1988), the carbon oxidized in the bottom water
(1.34 mol m− 2 yr− 1) can be used to estimate the bottom-water RT
from the consumption of oxidants. We ignore the flux of H2S into the
suboxic water and its subsequent oxidation. The concentrations of O2
and NO− 3 in the water entering at ca. 200 m depth (Müller-Karger
et al., 2001) are taken as their concentrations in the Caribbean at this
same depth (Morrison and Smith, 1990), namely 185 μM O2 and 5 μM
NO− 3 . The O2 is adjusted downward by 60%, the amount estimated as
consumed in the suboxic layer, based on the difference between the
10% of the Corg fixed by photosynthesis and assumed to settle out of
the photic zone and the 4.2% of the primary production settling to
275 m. The 10% used here is identical to the global average of Corg
settling out of the photic zone (Suess, 1980; Berger et al., 1988), which
in turn is close to the value for the Black Sea (Karl and Knauer, 1991).
The sequential consumption of the three oxidants in the bottom water,
In Eq. (4), the value 0.70 adjusts for the lower oxidative potential of
NO−3 owing to anammox reactions (Eq. (2)); 1.25 is the ratio of Corg
oxidized versus NO− 3 reduced. In Eq. (5), the 0.04 mol m
−3
of SO2−
4
reduced is simply the concentration of H2S in the bottom water; the
2 mol Corg mol− 1 SO2−
4 is the molar ratio of Corg oxidized versus SO4
2−
reduced. If we ignore the consumption of SO2− 4 by CH 4 oxidation, the
calculated rate of Corg oxidation in the bottom water of 1.34 mol Corg
m− 2 yr− 1 (70% of 1.92, or annual consumption rate of oxidants) gives
the following RT:
Bottom  water RT
−2 −2 −1
= ð82 + 5 + 88Þmol Corg m
1:34 mol Corg m yr
= 130 years; ð6Þ
approximating the 100 years calculated by Deuser (1973). The slightly
greater RT calculated here may represent uncertainty in the O2
consumed in the oxic and suboxic layer extending to 350 m depth
versus 275 m (the depth of the sediment traps), a variable H2S
concentration in the bottom water (Fanning and Pilson, 1972), and the
reduction of NO− +
3 to NH4 rather than to N2 (Eq. (4)). Despite the
permanent anoxic conditions in this shallow-silled basin, the bottom-
water RT reflects a rather vigorous renewal of bottom water compared
with the renewal of bottom water in the Black Sea (see Section 3.2.3).
3.1.2. Trace-metal budgets
Jacobs et al. (1987) suggested that the bottom water in the Cariaco
Basin enters at the same approximate depth as the water upwelling
into the photic zone. This may be explained by the importation of
bottom water largely in the summer and fall below the strong
thermocline that develops at 50 m depth (Müller-Karger et al., 2001;
Goñi et al., 2003). The strong thermocline and the depth of imported
water at this time of year limit upwelling and mixing into the
shallower depths, possibly enhancing water intrusion to depth. In the
winter and spring, much of the water imported probably mixes up
into the photic zone, owing to the collapse of the thermocline during
these seasons (Goñi et al., 2003). Such a seasonal difference in the
import of surface water and bottom water from a single depth in the
Caribbean accounts for the similarity in salinity and temperature of
the bottom water of the basin and of the Caribbean Sea at 100 to 200 m
depth (Richards, 1975), as well as the similarity in Mo and V
concentrations in the Cariaco Basin water column above the suboxic
78 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96

layer (Emerson and Huested, 1991; Fig. 7) and their concentrations in section to be calculated from bulk-sediment accumulation rates,
the open ocean. independently of their accumulation within the lithogenous fraction
First, consider the budget of trace nutrients in the water column (Piper and Dean, 2002). The Ni rate can then be compared to its
and sediment, focusing on Ni. It exhibits little or no depletion in the settling rate out of the photic zone incorporated in particulate organic
photic zone (Fig. 7), yet Collier and Edmond (1983) have measured a matter, again assuming a Ni concentration in plankton of 18 ppm
concentration in plankton of ca. 18 ppm. Its depth profile in the (Collier and Edmond, 1983) and a concentration of Corg in organic
Venezuela Basin, relative to that of HPO2− 4 , yields a concentration of matter of 36% (Redfield et al., 1963). For V and Mo, their accumulation
25 ppm in organic matter, for which the organic matter is assumed to rates are compared to their rates of removal from the bottom water
have Redfield stoichiometry (Redfield et al., 1963), i.e., 36% Corg. A as the hydrogenous fraction, which are given by their level of removal
concentration of 25 ppm is consistent with its measured concentra- from the bottom water of 65% and 15%, respectively, i.e., their
tion in average plankton of 18 ppm. Although we are not able to concentration in the surface oxic water versus their concentration in
calculate its rate of input into the photic zone, owing to a weakly the bottom water (Emerson and Huested, 1991), and the bottom-
constrained upwelling rate, we can compare its availability in the water RT.
upwelling water to its uptake by phytoplankton, relative to that of The deposition of marine Ni is given by the settling flux of Corg out
−
HPO2−4 , or NO3 . As HPO4
2−
and NO− 3 are completely removed in the of the photic zone (10% of primary productivity) and the mean Ni
photic zone on a seasonal basis, both are limiting nutrients to primary (Collier and Edmond, 1983) and C org (Redfield et al., 1963)
productivity. The Ni:HPO2−4 ratio in the water fluxing into the basin at concentrations in phytoplankton.
ca. 200 m depth is 0.12:190 μg/µg (Jacobs et al., 1987), or 0.00063. The

same ratio in plankton is 18:0.26 × 10− 6, or 0.000067. Thus, only about Ni deposition rate = 550 g Corg m
−2
yr
−1
× 0:10
10% of the Ni made available through upwelling is utilized by

× 18 cg Ni
0:36 g Corg
phytoplankton, in agreement with only a slight depletion in the
−2 −1
photic zone (Fig. 7). The same calculation for Cd reveals that 90% of = 2750 cg Ni m yr ; ð7Þ
the Cd upwelling into the photic zone is taken up by phytoplankton,
accounting for its near complete depletion in the photic zone. This rate can be compared with its accumulation rate on the seafloor,
Marine Ni is the preferred proxy for this biogenic fraction in the the product of the mean bulk-sediment accumulation rate and the
sediment, as it has only the one marine source, biogenic detritus. That marine Ni concentration in the sediment:
there is little input of Ni into the sediment from the anoxic water
−2 −1 −1
column is shown by its uniform concentration in the bottom water of Ni accumulation rate = 138 g m yr × 19 cg Ni g
this and other anoxic basins (Kremling, 1983; Jacobs et al., 1985; = 2620 cg Ni m
−2
yr
−1
: ð8Þ
Haraldsson and Westerlund, 1991), although its removal under
sulfidic conditions as the sparingly soluble sulfide would have been The accumulation rate of Corg itself is 6.9 g m− 2 yr− 1 (Piper and Dean,
predicted. Conversely, the seawater profile of Cd reflects its uptake in 2002), which has a concentration in the upper few meters of the
the photic zone by phytoplankton, remineralization below the photic sediment of 5 wt.% (±1%). This represents only 1.25% of primary
zone of the organic matter with a Cd concentration of 12 ppm productivity, suggesting no enhancement of Corg preservation under
(Brumsack, 1986; Collier and Edmond, 1983), and its additional anoxic bottom-water conditions, as deduced by Thunell et al. (2000).
removal from the bottom water as a hydrogenous fraction. Copper and For marine Mo, its deposition from the bottom water between 300
Zn have similar dual pathways in the ocean to that of Cd. and 900 m depth onto the ca. 900 m deep saddle, represented by the
Molybdenum has a concentration of ca. 10.5 ppb in the uppermost removal of 15% of its inventory in the bottom water (Fig. 7), is:
300 m of the water column (Fig. 7), similar to its concentration in the
open ocean (Collier, 1985) and, presumably, in the Caribbean. It shows Mo deposition rate



a step decrease (Fig. 7) of 15% at 300 m depth (Emerson and Huested, = 10:5 cg Mo L
−1 5
× :15 × 6 × 10 L m
−2

115 yr
1991) and remains lower throughout the bottom water than its −2 −1
concentration at the surface. Vanadium shows a similar profile to that = 8300 cg Mo m yr ; ð9Þ
of Mo, except that it decreases smoothly through the suboxic zone,
reaching a concentration in the anoxic bottom water of 35% of its at a mean bottom-water RT of 115 years. This compares closely with
surface value (Emerson and Huested, 1991). As both metals are weakly its accumulation rate in the sediment:
bioreactive and strongly redox reactive, their enrichment in the −2 −1 −1
sediment is largely as a hydrogenous fraction; they should serve as Mo accumulation rate = 138 g m yr × 78 cg Mo g
ideal proxies of bottom-water anoxia. = 10; 600 cg Mo m
−2
yr
−1
: ð10Þ
The accumulation of the third sediment fraction, the lithogenous
fraction along with its complement of trace elements, is seasonally Similarly, the deposition of V from bottom water is 9300 μg m− 2 yr− 1,
variable, owing to variable stream runoff from the coast of Venezuela and its accumulation rate as a hydrogenous fraction is 7200 μg m− 2 yr− 1.
that leads to an increased flux of lithogenous sediment into the basin Although sediment-trap studies in the Black Sea (Crusius et al., 1996),
that is out of phase with primary productivity and the flux of Corg to Saanich Inlet (François, 1988), and the Cariaco Basin (Calvert, Piper, and
the seafloor (Goñi et al., 2003). The higher production and settling Thunell, in preparation) reveal that Mo removal from the bottom water is
flux of biogenous components (CaCO3, opal, and organic matter) in restricted to the benthic boundary layer in these anoxic basins (elevated
winter and spring and the higher delivery of lithogenous (siliciclastic) concentrations are not captured in sediment traps), its accumulation rate
material in summer and fall leads to the deposition of the on the seafloor (Eq. (10)) equals its removal rate from the water column
compositionally distinct laminae in the sediment on the centrally- (Eq. (9)), which is calculated from its depletion in the entire 600 m of
located saddle (Hughen et al., 1996). Trace elements and major- anoxic water above the core site (Piper and Dean, 2002). The
element oxides that can serve as proxies of the lithogenous fraction hydrogenous V fraction and the biogenous Ni fraction are both captured
include the rare-earth elements, Th, Ga, Co, Li, Rb, Cs, K2O, Fe2O3, and by sediment traps located within the water column (Calvert, Piper, and
of course Al2O3 (Piper and Dean, 2002). Thunell, in prep.). In other words, their settling fluxes equal their
The normative modeling scheme described earlier allows the deposition rates. The close agreement between the rates of accumulation
accumulation rates of the marine fraction of the trace elements, on the seafloor of the marine fractions of Mo, Ni, and V in the sediment
specifically Mo, Ni, and V, in the uppermost 50 cm of the sediment with their rates of delivery to the seafloor in this modern basin, based on
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 79

the level of primary productivity (Ni) and their distributions in, and RT of,
bottom waters (Mo and V) supports the modeling of trace-element
accumulation rates in sediments to provide estimates of the levels of
primary productivity in the photic zone and the exchange rate of bottom
water with the Caribbean.
delivered by the Danube (ca. 50%), the Dnestr and Dnepr (together ca.
40%), and smaller rivers (10%). These inputs of fresh water and the
difference between evaporation (353 km3 yr− 1) and precipitation
(300 km3 yr− 1) maintain mass balance of salt and water, driving the
estuarine circulation between the Black Sea and Sea of Marmara.

3.2. The Black Sea 3.2.1. Primary productivity

Primary productivity in the Black Sea is ca. 210 g Corg m− 2 yr− 1
The Black Sea was isolated from the Mediterranean during the last (Sorokin, 1983; Karl and Knauer, 1991). Production is seasonally
glacial maximum, when sea level stood ca. 130 m lower than its variable, diatoms blooming in February–May and coccoliths blooming
present level (Caspers, 1957; Strakhov, 1971; Degens and Ross, 1972; in June–October (Sorokin, 1983; Honjo et al., 1987). Lithogenous
Fairbanks, 1989). Post-glacial eustatic sea-level rise connected the particle fluxes are highest in November–May, the seasonal change in
Mediterranean with the Black Lake when global sea level reached the the composition of the settling material leading to the formation of
level of the Bosporus sill, initiating the influx of saline waters and compositionally distinct laminae in the bottom sediment (Müller and
transforming the Black Sea into the modern, intermediate-salinity, Blaschke, 1969; Müller and Stoffers, 1974). Although these alternating
estuarine basin. Hydraulic modeling has suggested that sea water biogenous and lithogenous laminae may constitute annual varves
invasion began roughly 1000 years after sea-level reached the level of (Arthur et al., 1994), reliably counting them in abyssal basin cores is
the Bosporus sill at 40 m depth (Lane-Serff et al., 1997), a delay somewhat tenuous (Crusius and Anderson, 1992).
required to set up a sufficient hydraulic head above the level of out- Primary productivity is sustained by the import of nutrients into
flowing fresh water from the Black Sea so that two-layer flow could be the photic zone from approximately 50 m depth. The NO− 3
established. The accumulation of brackish and marine deposits, concentration at this depth, which we take as the limiting nutrient,
beginning with the Black Sea sapropel, began at around 7500 to is 8 μM (Codispoti et al., 1991). The average fluvial NO− 3 input is
7800 years BP (Jones and Gagnon, 1994; Arthur and Dean, 1999). obtained from the product of the mean river concentration prior to the
Today the narrow Bosporus Strait connects the basin to the eastern last few decades (Maybeck, 1982) and the river flux:
Mediterranean and the Sea of Marmara. It is the largest permanently
− −1 3 −3 11 3 −1
anoxic basin in the marine realm today. It has been variously described Riverine NO3 flux = 15 cmol L × 10 L m × 3:52 × 10 m yr
as “the type euxine” (Byers, 1977), the “type anoxic basin” (Glenn and ¼5:3 × 10
15
cmol NO3
−
yr
−1
: ð11Þ
Arthur, 1984), “the definitive anoxic basin” (Murray, 1991), and “a freak
of palaeogeography” (Tyson, 2005). Its isolation from the open ocean Anthropogenic inputs of NO− 3 and other nutrients by the rivers
and the permanently anoxic state of its bottom waters render the Black entering the Black Sea have increased this value possibly by as much
Sea a highly informative geochemical model of ancient basins. as 10-fold in the last few decades (Maybeck, 1982; Oguz, 2005), but
The salinity contrast between surface and deep waters of the Black we ignore this perturbation here. An estimate of the NO−3 input from
Sea induces a strong density stratification, maintaining anoxia below the Sea of Marmara (Polat and Tuğrul, 1995) yields:
an intense pycnocline at ca. 100 m depth, although the depth of the
−
pycnocline has likely decreased in the past few decades (Murray et al., Bosporus NO3 input



1989). The surface 50 m has a salinity of about 17.9‰, which increases 11 3 −1 3 − −3
= 3:05 × 10 m yr × 7 × 10 cmol NO3 m
sharply to 21‰ at ca. 100 m and then more gradually to 22.5‰ below
15 − −1
1750 m. A suboxic layer of cold intermediate water (CIL) lies between = 2:1 × 10 cmol NO3 yr : ð12Þ
the oxic uppermost 50 m and the anoxic bottom water at 100 m
(Codispoti et al., 1991). The CIL forms largely in the northwestern The total import of dissolved NO−3 is therefore ca. 7.4 × 10
15
μmol yr− 1.
margins of the basin by winter cooling and spreads throughout the sea Although the two inputs are similar in magnitude, the enclosed
(Murray et al., 1991; Özsoy and Ünlüata, 1997). Oxygen and H2S go to environment of the Black Sea and shallow sill cannot be compared to
zero in this suboxic layer (Fig. 3). Nitrate, HPO2− and H4SiO4 reach open-ocean environments, where above we noted that the river input
4
maxima in the upper reaches of the layer (Fig. 7), NO− for an open-ocean environment was minor, even in coastal areas off
3 through
nitrification of settling organic matter before decreasing to zero via major rivers.
denitrification immediately above the anoxic bottom water (Codispoti This NO−3 input into the Black Sea is insignificant in comparison to

et al., 1991). As observed in the Cariaco Basin, anammox reactions the annual NO− 3 demand of phytoplankton. This demand can be

lower NH+ − estimated from the area of the sea of 420,000 km2 and the primary
4 and NO2 to zero at this same depth (Kuypers et al., 2003).
Bottom water in the basin is a mixture of Mediterranean water that productivity of 210 g Corg m− 2 yr− 1, assuming Redfield stoichiometry
enters through the Bosporus and the suboxic CIL, in the approximate for the organic matter (Redfield et al., 1963):
ratio of 1:3.3 (Murray et al., 1991). The penetration depth of much of −
Phytoplankton NO3 demand
the inflowing Mediterranean water is limited largely to the upper


500 m, leaving the deeper basin waters progressively more isolated, ½ 11 2
= 4:2 × 10 m × 210 g Corg m


−2
yr
−1

with a RT possibly of several thousand years (Özsoy and Ünlüata, −

× 0:28 g NO3
0:36 g Corg


1997). The inflowing Bosporus plume delivers salt and O2 into the
deeper layers by the lateral injection of plume waters (Ivanov and
4 − −1
× 1:6 × 10 cmol NO3 g NO3
−

15 − −1
Samodurov, 2001) rather than by slow vertical diffusion. However, the = 1100 × 10 cmol NO3 yr : ð13Þ
flux of O2 is insufficient to prevent the built up of H2S, which has
concentrations currently reaching 100 μM at 200 m and increasing to The NO− −
3 demand is much larger than the external NO3 supply
380 μM at 2200 m depth. The bottom 300–400 m of the deep-water (Eqs. (11) and (12)) and can only be met by nutrient recycling in the
column, below 1750 m, is isothermal and isohaline (Murray, 1991). surface water and the vertical movement of waters from below the
The average export rate of waters into the Sea of Marmara through surface photic layer by upwelling and vertical mixing. This is
the Bosporus Strait, between the sea surface and 25 m, is ca. 605 km3 analogous to the nutrient supply to coastal waters of the open
yr− 1 (Özsoy and Ünlüata, 1997). Sub-surface water is imported into ocean, where upwelling oceanic waters represent the dominant
the Black Sea below this exported surface water to 40 m depth, at a source of nutrients, here equal to 110 × 1015 μmol NO−3 yr
−1
, or 10%
rate of 305 km3 yr− 1. An average fresh-water influx of 352 km3 yr− 1 is of the demand of primary productivity.
80 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96

The rate of import of nutrients in support of new production is 3.2.3. Bottom-water residence time
simply the seawater flux necessary to deliver this amount of NO− 3 to The RT of the bottom water can be calculated from the oxidants
the photic zone, i.e., to the mixed layer lying immediately above the consumed in a parcel of water (Eqs. (15)–(17)) versus the rate that
CIL: Corg is oxidized, or the rate that Corg settles out of the photic zone. If
the small fraction of Corg that escapes oxidation in the water column
Upwelling ðmixingÞ rate and eventually accumulates on the seafloor is ignored, then
h
 i
15 11 −2 −1
= 110 × 10
4:2 × 10 cmol m yr
−2
h
i RT = ½ð635 − 490Þ + ð15 − 9Þ + ð1600Þmol Corg mðoxidants reducedÞ
3 −3 −1 ð14Þ

8 × 10 cmol m = 33 m yr : −2 −1

½210 × 0:10
12mol m yrðrate of Corg oxidizedÞ
−2 −2 −1
This should represent a close estimate as the input from rivers and loss ¼1750 mol Corg m
1:75 mol Corg m yr = 1002 yr:
by the export of surface water into the Sea of Marmara may approxi- ð18Þ
mately balance. The RT of surface water is then ca. 1 to 2 years. As Lee
et al. (2002) reported a RT for water between 80 and 120 m in the Adjustments to the consumption of O2 (635 − 490) and NO− 3 (15 − 9)
suboxic layer of ca. 5 years, the 1 to 2 years seems a reasonable represent mixing of suboxic CIL with Mediterranean water in the ratio of
estimate for the photic zone. 3.3:1 (Murray et al.,1991) to form the bottom water. Unlike conditions in
the Cariaco Basin, both terms are small compared to the SO2− reduction
3.2.2. Oxidant balance in bottom waters term of 1600 mol Corg m− 2. The RT derived in this way is significantly
As we showed earlier for the Cariaco Basin, the consumption of the greater than the 387 years estimated by Murray et al. (1991), lies within
major oxidants during oxidation of Corg can be estimated from the the 1000 to 2000-yr range reported from radiocarbon measurements
utilization of dissolved O2, NO− 3 and SO4
2−
in the remineralization of (Ostlund, 1974), but is lower than the several thousand years advanced
organic matter as it settles to the seafloor. The O2 concentration in the by Özsoy and Ünlüata (1997), Grégoire and Stanev (2001), and Stanev
water imported from the Mediterranean is taken as 290 μM, its (2005) and the 2500 to 3000 years estimated by Anderson and Fleisher
approximate solubility at 8 °C and 35‰ (Weiss, 1970). The contribution (1991) from the U budget.
of NO− 3 reduction to the oxidation of organic matter is much less than An alternative estimate of the RT can be made from the export (or
that of O2 per unit volume of water, owing to the large difference in their import) of salt versus the salt inventory of the basin, i.e., the rate of salt
respective concentrations in the imported water. The maximum NO− 3 replacement, a condition for steady state.
concentration in the Black Sea (8 μM) is at about 60 m depth, the upper
part of the CIL, or suboxic zone. As noted above, the maximum is due to RT = ½volume × mean salt concentration
½salt export rate



oxidative regeneration (nitrification) of settling organic detritus 5 3 3 −1
= 5:3 × 10 km × 22:2x
605km yr × 17:9x = 1100yr:
(Codispoti et al., 1991) and import of water from the Sea of Marmara,
below which it and the other forms of fixed-N go to zero at the suboxic– ð19Þ
anoxic interface. The SO2−4 contribution to the oxidation of Corg in the
bottom water is given by the concentration of H2S (380 μM). The The RT of the surface and near-surface waters will be less than this
sequence of reactions for the oxidation of Corg can be quantified in terms value, whereas the RT of bottom water will be greater. Indeed, Lee et al.
of the reduction of major oxidants in the lower 2150 m of the water (2002) reported that the RT of water in the upper part of the water
column, i.e., below the photic zone, as was outlined for the Cariaco Basin column increased to 625 years with depth through the uppermost
(Eqs. (3)–(5)). We again ignore the flux of H2S into the suboxic water 500 m. Although this and the other measurements fail to constrain
and its subsequent oxidation. tightly the RT of bottom water, the estimates summarized here suggest
that the mean RT lies in the range of 1500 to 2500 years.
Oxic respiration :
h i 3.2.4. Trace-metal budgets in bottom waters
−3 −1
0:290 mol O2 m × 2150 m × 1:0 mol Corg mol O2
The distributions of trace metals in the Black Sea water column are
−2
= 635 mol Corg m : ð15Þ similar to their distributions in the Cariaco Basin (Fig. 7). Dissolved
Mn and Fe display maxima just below the oxic–anoxic interface, due
Suboxic respiration : to the reductive dissolution of particulate oxyhydroxides (as Mn(IV)


i and Fe(III)) settling from the oxic near-surface waters into the anoxic
½ 0:008 mol NO−
3 m
−3
× 0:70 × 2150 m × 1:25 mol Corg mol
−1 −
NO3 water (Brewer and Spencer, 1974; Haraldsson and Westerlund, 1991;
−2
= 15 mol Corg m : ð16Þ Lewis and Landing, 1992). Iron in the anoxic zone as Fe(II) is close to
equilibrium with FeS (mackinawite) and Fe3S4 (greigite) (Landing
Anoxic respiration : and Lewis, 1991), consistent with the removal of dissolved Fe as Fe
h

i “monosulfide”. Particulate Mn and Fe have complementary maxima
2− −3 −1 2−
0:38 mol SO4 m × 2100 m × 2 mol Corg mol SO4
at the base of the oxic zone, immediately above their dissolved
−2
= 1600 mol Corg m : ð17Þ concentration maxima (Brewer and Spencer, 1974). There may also be
direct supply of Fe to the central basin from the basin margins
Adjusting for units gives 1090 μM Corg as the sum of carbon added to (Wijsman et al., 2002; Lyons and Kashgarian, 2005). Dissolved Cu and
the bottom water. This value is only ca. 15% lower than the measured Zn decrease in concentration across the suboxic–anoxic interface
increase of CO2 in the bottom water over its concentration in the (Haraldsson and Westerlund, 1988, 1991; Lewis and Landing, 1992),
surface 100 m and 20% higher than that attributed to the oxidation of supporting the interpretation of their removal from seawater in the
Corg by Goyet et al. (1991). The excess can be attributed to entrainment anoxic zone, although they are undersaturated with respect to Cu2S
of CIL, the Black Sea water that mixes with imported Mediterranean and ZnS, respectively (Landing and Lewis, 1991). Cadmium and Pb
water in the ratio of 3.3:1 (Murray et al., 1991) to form the deep water also decrease in concentration across the suboxic–anoxic interface.
of the basin. The adjusted sum of oxidants reduced in the water Both are close to saturation with respect to CdS and PbS, respectively;
column is then equivalent to the CO2 generated from the oxidation of they are likely removed from solution as these, or similar, phases
Corg. Seventy percent of the Corg in the Black Sea is oxidized by SO2−
4 , (Landing and Lewis, 1991). Nickel exhibits little variation with depth
compared to 50% in the Cariaco Basin (Eq. (5)). (Brewer and Spencer, 1974; Haraldsson and Westerlund, 1988),
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 81

although a ca. 50% decrease is reported by Landing and Lewis (1991). an adsorbed phase (Jacobs et al., 1987; Landing and Lewis, 1991). Its
It has a uniform profile in other anoxic basins (Jacobs et al., 1985, export from the photic zone then equals its depositional rate as a
1987). We have no explanation for the difference in the measure- seawater-derived biogenous fraction (Piper, 1994), or 1050 μg Ni m− 2
ments of Ni in the Black Sea by Landing and Lewis versus yr− 1. At a mean bulk-sediment accumulation rate of 38.5 g m− 2 yr− 1
measurements by the other groups, although the weight of evidence (Calvert et al., 1991), this gives the following seawater contribution to
from this and the other basins favors the invariant vertical its sediment concentration:
concentration profile for this element in anoxic basins.
Dissolved Co shows an increase in concentration coincident with Marine Ni sediment concentration
the dissolved Mn and Fe maxima due to its release from dissolution of −2 −1 −2 −1
= 1050 cg Ni m yr
38:5 g m yr = 27 ppm: ð22Þ
oxyhydroxide phases, mostly of Mn, settling out of the oxic–suboxic
zone (Haraldsson and Westerlund, 1988, 1991; Lewis and Landing, Of the Ni in the surface sediment of 122 ppm (Calvert, 1990), 22% is
1992). In both the photic zone and anoxic zone, its concentration is derived from the photic zone and delivered to the sediment by a
low (ca. 0.2 and 0.25 nM, respectively, versus 1 to 4 nM between 200 biogenous vector. Measurements of the accumulation rate of Corg in
and 400 m). It is undersaturated with respect to simple sulfide phases. the surface sediments show that only about 1% of primary productiv-
Although some of the Co is associated with particulate Al2O3 in ity is buried (Calvert et al., 1991). This is reflected by the higher Corg:Ni
bottom-water suspended phases, some fraction is apparently ratio in plankton (0.020 g μg− 1) than in the sediment (0.0019 g μg− 1).
adsorbed onto particulate Fe (Lewis and Landing, 1992). Even so, its Molybdenum and V have depth profiles in the Black Sea (Emerson
extremely low concentration in the water column and slightly and Huested, 1991) similar to those of Cd, Cu, and Zn, indicating their
elevated concentration in the bottom water precludes measurable removal from the bottom water. The Mo concentration in the bottom
Co enrichment in the sediments above a lithogenous input, even if water is as little as 10% its concentration in the surface and near
totally removed from the bottom water. surface water. Similar to the Cariaco Basin, no marine Mo fraction is
These observations suggest that Fe, Cd and Pb are deposited from captured in sediment traps with settling particulate debris in the
the anoxic waters of the Black Sea by precipitation of their solid anoxic waters of the Black Sea, whereas the metal is strongly enriched
sulfides. Copper and Zn, which also have much lower concentrations in the bottom sediments above a lithogenous contribution. Again, its
in the anoxic zone, are likely deposited as sulfide complexes (e.g. MeS removal from the water column is apparently restricted to the benthic
(HS)−) and adsorbed onto solid phases, possibly onto FeS2, both being boundary (Emerson and Huested, 1991, Crusius et al., 1996). None-
undersaturated with respect to their respective sulfides (Landing and theless, its depletion throughout the anoxic region of the water
Lewis, 1991; Lewis and Landing, 1992). Finally, Co and possibly Ni are column suggests that the entire water column contributes to its ele-
undersaturated and probably exist as dissolved sulfide complexes in vated concentration in the sediment. Vanadium, as discussed earlier, is
the anoxic waters; their possible removed from the anoxic water is present as VO2(OH)2− 3 in oxic seawater and is reduced to the much
insignificant relative to their accumulation on the seafloor. That some, more strongly adsorbed VO(OH)− 3 under suboxic and anoxic condi-
but not all, redox-sensitive metals are removed by particle scavenging tions (Sadiq, 1988; Wehrli and Stumm, 1989; Emerson and Huested,
in anoxic waters, rather than by direct precipitation of their sulfide 1991), leading to its removal from the water column, its presence in
phases (Haraldsson and Westerlund, 1991), is supported by theore- sediment traps, and its deposition on the seafloor by adsorption reac-
tical studies of Dyrssen (1985). And finally, deposition of Ni from the tions under both suboxic and anoxic redox conditions.
water column is tied to the Corg cycle, i.e., to primary productivity. Although they are enriched in the sediments above a lithogenous
Similar to the calculations advanced for the Cariaco Basin, the input, the accumulation rates of the hydrogenous fractions of both
fluxes of several trace elements through the water column to the Mo and V from the bottom water are unexpectedly low, Mo more so
sediments as: (1) a biogenous fraction (Ni); (2) a hydrogenous than V. For Mo, its import rate from the Sea of Marmara, in which its
fraction added to the sediments through inorganic redox reactions (V concentration is 10 ppb (Pilipchuk and Volkov, 1974), is:
and Mo); or (3) by both mechanisms (Cd, Cu, Zn) are determined from


their supply and removal rates from the water column and an 3 −3
Mo import rate = 10 × 10 cg Mo m
understanding of redox processes within the water column and the

3 −1 9 3 −3
bottom sediments. The rate that the micro-nutrient Ni is imported × 305 km yr × 10 m km


5 2 6 2 −2
into the photic zone (expressed as an upwelling rate) is simply:
4:2 × 10 km × 10 m km
= 7260 cg m
−2
yr
−1
: ð23Þ
−1 3 −3
Ni upwelling rate = 33 m yr × 0:49 × 10 cg Ni m
= 16; 200 cg m
−2
yr
−1
: ð20Þ Its concentration profile in the bottom water suggests that greater than
ca. 90% of its import is eventually deposited on the seafloor, correspond-
Loss of Ni from the photic zone via settling of Corg, namely the export ing to a removal rate from the anoxic water of 6500 μg m− 2 yr− 1. Its
of 10% of primary productivity, the global export rate as was adopted accumulation rate, however, is a small fraction of this amount.
earlier, or 21 g Corg m− 2 yr− 1 with the Ni:Corg concentration ratio of


18 ppm:36%, is: −1 −2 −1
Mo accumulation rate = 50 cg g × 0:85 × 38:5 g m yr

 = 1640 cg Mo m
−2
yr
−1
; ð24Þ
−2 −1 −1
Ni loss = 21 g Corg m yr × ð18
0:36Þcg g
−2 −1
= 1050 cg Ni m yr : ð21Þ where the bulk Mo concentration in the surface sediment is ca. 50 ppm
(Volkov and Fomina, 1974). Approximately 10% is contributed by the
Again, Ni is not a limiting nutrient, although it is an essential nutrient. lithogenous fraction, based on the Mo:Al2O3 ratio of WSA and the Al2O3
For a bottom-water RT of 1500 to 2500 years, we might have concentration in the sediments, and 5% is contributed by biogenic debris,
expected to see as much as a doubling of Ni in the bottom water in based on a maximum Mo:Corg ratio of phytoplankton (Brumsack, 1986)
response to the remineralization of organic matter settling through and the rate of deposition of Corg obtained from the accumulation rate of
the water column. The lack of such a build up in this and other anoxic marine Ni.
basins (Jacobs et al., 1985, 1987; François, 1988; Haraldsson and The Mo accumulation rate then represents only 20 to 25% of the
Westerlund, 1988, 1991) suggests that the organically bound Ni input rate through the Bosporus. To account for the discrepancy, most
exported from the photic zone is deposited on the seafloor largely as of the Mo imported into the Black Sea must be exported back into the
82 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
Sea of Marmara in the surface outflow (Deuser, 1974). In support of
this interpretation, the maximum concentration of Mo in the water
column of the Black Sea (ca. 110 nM) is in the very surface water
(Emerson and Huested, 1991), the water that is exported back into
the Sea of Marmara under the estuarine circulation of the basin. As
little as 20% of the imported Mo from the Sea of Marmara must be
deposited on the seafloor (1450 μg m− 2 yr− 1) to achieve agree-
ment with its accumulation rate. Vanadium has a similar seawater
profile to that of Mo (Emerson and Huested, 1991). As the chemistry
of the uppermost part of the water column has been drastically
altered in the past several decades (Halim, 1991), it is not now pos-
sible to know the natural concentration of trace elements in the
oxic water in previous years, but the trace elements would also have
been exported largely back into the Sea of Marmara by the estuarine
circulation.
The disparity between the inputs and accumulation rates of these
metals apparently reflects the small fraction of imported water from
the Sea of Marmara that actually ventilates the Black Sea at depth. The
sill depth in the Bosporus must play a central role in limiting the net
flux of Mo, V and other trace metals into the bottom water such that
the import of these metals is only slightly greater than their export in
the surface water.
3.3. Summary
Agreement between the uptake of Ni in the photic zone by
plankton and its deposition on the seafloor, in both the Cariaco Basin
and Black Sea, supports its use as a proxy for the rate of primary
productivity in ancient basins whose bottom waters were O2 depleted.
Likewise, the estimates of the accumulation of Mo and V in the two
modern basins support their use as proxies of bottom-water redox.
The 4 to 5-fold higher accumulation rates of Mo and V on the seafloor
of the Cariaco Basin than in the Black Sea are probably due to
differences in the circulation of the two basins that may largely reflect
their sill depths. Both basins have an estuarine circulation. In the Black
Sea, the imported water enters at a depth of 25 to 40 m. Although
some fraction of this water clearly descends to depth, much of the
imported water must be mixed into the photic zone and exported back
into the Sea of Marmara with its complement of trace elements.
Evidence for the mixing of the imported water and the CIL is the
maintenance of the salinity of surface water. The volumes of imported
water from the Sea of Marmara and of riverine fresh water are
approximately equal, with salinities of 35.8‰ and 0‰, respectively;
the salinity of a mixture of the two should be 17.9‰, which is the
salinity of the surface water (Özsoy and Ünlüata, 1997). An
exceptionally low accumulation rate for both Mo and V on the
seafloor simply suggests loss of much of the trace-element inventory
of the imported water by the export of surface water, supporting the
suggestion that the mean bottom-water RT is likely significantly
greater than 1000 years.
The contrast in sill depth between the Cariaco Basin (145 m) and
Black Sea (40 m) is likely critical to the mixing of imported waters. The
different hydrography of the two basins leads to the interpretation that
ancient basins that exhibited O2 depletion in the bottom water for
extended periods of time and that now have sediment concentrations of
marine V and Mo in the range of several 100 ppm probably had an
exchange of seawater with the open ocean possibly exceeding even that
of the Cariaco Basin, owing to the presence of a deep sill or no sill at all.
4. An ancient marine environment
Piper and Isaacs (1994, 1996), Piper (2001), and Perkins et al.
(2008) used the normative modeling approach described in this paper
to interpret the marine environments of deposition of black shales
ranging in ages from Late Devonian to Miocene, and Pleistocene
sediments from the Sea of Japan. Rather than reiterate these results,
we have elected to model the upper Jurassic KCF of northwestern
Europe (Figs. 1 and 2) in order to derive levels of primary production,
water column redox, and hydrography in the Kimmeridge Sea during
the deposition of the cyclical organic-rich/organic-poor sediment
lithologies of this deposit. The KCF in England and correlative
formations in northern France are some of the most thoroughly
examined black shales in the world, owing to the large oil source-rock
potential of coeval rocks in the North Sea grabens. A comprehensive
review of this literature is beyond the scope of this paper. Rather,
following a brief summary of the principal features of the formation,
we present our interpretations of the water-column dynamics under
which the KCF was deposited in the distal environment of the
Cleveland Basin in Yorkshire, England and then compare this
environment with the time correlative units deposited in the proximal
environment of the Boulonnais Basin in northern France. The data
have been published by Tribovillard et al. (2005), who has kindly
provided access to this valuable data set. One set of samples was taken
from cores at three sites in the Cleveland Basin; the second set of
samples was collected from the correlative formations that outcrop in
the cliffs along the coastline immediately north of Boulogne. One
centimeter-thick samples were taken at a spacing of 3 to 5 samples per
10 m of section in the Cleveland Basin and ca. 6 samples every 10 m at
the Boulonnais site. Two sections in the cores from the Cleveland
Basin, referred to as primary cycles, were sampled on a centimeter
scale.
As we have discussed previously, possible bathymetric or paleo-
ceanographic differences between modern and ancient basins should
not invalidate a comparison of their geochemical records. The
processes that are central to the relationship between the geochem-
istry and hydrography of the water column and the accumulation of
Corg and trace metals on the seafloor are quite separate from the
bathymetry of the basin, whether the “basin” had an actual
bathymetric expression or was an epeiric sea, possibly with no sill.
However, the texture and fine-scale laminar nature of the KCF, lack of
extensive bioturbation, and preservation of delicate articulated
bivalves commonly along bedding planes (Tyson et al., 1979) suggest
a closer similarity of the depositional conditions of the KCF to the two
prominently-silled anoxic basins discussed here than to those of the
OMZs of modern continental margins.
A comparison of the marine environment in the Cleveland Basin
with the depositional environment in the Wessex Basin, approxi-
mately 400 km to the south, where the type Kimmeridge section is
located (Cox and Gallois, 1981), is problematic. Whereas the
sedimentology and physical properties of the coastal outcrops in
southern England have been studied extensively (e.g., Tyson et al.,
1979; Oschmann, 1988a,b; Wignall and Hallam, 1991; Wignall, 1994;
Tyson, 2004; Weedon et al., 2004), to our knowledge no analytical
investigation has been carried out on these rocks comparable to this
investigation of the Yorkshire cores. Likewise, outcrops in the
Cleveland Basin are apparently of such quality that they allow for a
much poorer examination of the physical properties of the formation
than in the Dorset sections (Cope, 1974). A detailed examination of the
chemical composition of drill cores from the Wessex Basin and the
physical properties of cores from the Cleveland Basin will eventually
correct this discrepancy. In the meantime, we are aware that some of
our interpretations of the environment of deposition of the KCF, based
on the geochemistry of the cores from the Cleveland Basin, may not
apply to the conditions of deposition in the Wessex Basin, based on
the descriptions of outcrops and the paleontological record, more so
than on the geochemistry.
4.1. General description
Deposits of the KCF in the Cleveland Basin represent one of the
most complete sections of this formation that accumulated in the
distal part of an epeiric sea during the Late Jurassic. It was but one
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
basin in an epeiric sea that extended from the Barents Sea to the
English Channel (Hallam, 1975). Descriptions and interpretations of
the stratigraphy, sedimentology, paleoecology, geochemistry and
paleoceanography of the formation can be found in Cox and Gallois
(1981), Oschmann (1988a,b, 1990), Miller (1990), Wignall (1990,
1994), Macquaker and Gawthorpe (1993), Herbin et al. (1995), Proust
et al. (1995), Tyson (1996, 2004), Wignall and Newton (2001),
Morgans-Bell et al. (2001), Tribovillard et al. (2001, 2005), Jenkyns
et al. (2002), Lees et al. (2004). The rocks are laminated at several
horizons (Oschmann, 1988b; Wignall, 1991; Macquaker and
Gawthorpe, 1993) and the preservation of delicate bivalves, 75%
articulated, and restricted trace fossils commonly along bedding
planes (Tyson et al., 1979; Wignall, 1994) suggest little sediment
reworking and tranquil bottom waters. The environment was
interrupted periodically by bottom scouring possibly from storm
events, as evidenced for example, by rip-up clasts and hummocky
cross stratification (Wignall, 1989). A dysaerobic benthic fauna
(Oschmann, 1988a; Wignall, 1990) is suggestive of a bottom water
strongly depleted in O2, similar to the water at intermediate depths on
the continental shelves of Peru (Codispoti, 1980), the Gulf of California
(Calvert, 1964), Namibia (Kuypers et al., 2005), and the Arabian
Peninsula (Codispoti, 1980), and to the seafloor in the Santa Barbara
Basin within the California Borderland (Soutar and Crill, 1977).
Cycles of organic enrichment on several scales are a notable feature
of the KCF. Five organic-carbon-rich intervals (ORIs) several meters
thick are present in both basins, occurring at the same horizon, in the
same ammonite zones (Herbin and Geyssant, 1993; Herbin et al., 1995;
Weedon et al., 2004). Nested in both the ORIs and intervening
organic-poor intervals (OPI) are units that Tribovillard et al. (2005)
refer to as “primary cycles” up to 1.2 m thick. On an even finer scale are
millimeter thick laminae. As is the case with many other black shales,
the high Corg contents of these rocks, the laminated structure,
restricted benthic fauna and occasional complete lack of benthic
fossils, together with the enrichment of several redox-sensitive trace
elements above a lithogenous contribution have been interpreted as
indicating accumulation under O2-depleted bottom waters (Wignall
and Myers, 1988; Tribovillard et al., 2005). Evidence for time intervals
of high productivity, especially for some of the coccolith-bearing
limestone bands, has also been reported (Lees et al., 2004; Pearson
et al., 2004; Weedon et al., 2004; van Dongen et al., 2006).
Deposition occurred in a series of basins (Hallam and Bradshaw,
1979), possibly shallow-silled, each with perhaps a different depth
that varied through time (Wignall and Hallam, 1991) in response to
sedimentation, eustatic sea level changes, and basin subsidence and
emergence. It is not possible to establish the depth of the Cleveland
Basin with any certainty. Tyson et al. (1979) suggested a depth of a few
hundred meters; Weedon et al. (2004) proposed a depth that varied
between 50 and 75 m; Wignall (1989), Stow et al. (2001), and Bjerrum
et al. (2001) proposed a depth less than 200 m, all based more or less
on the depth of wave base and the presence of bottom-current and
storm-induced sedimentary features.
Oschmann (1990) has questioned the prominence of high-energy
sediment features, owing to their possible over-representation
relative to laminated sediment, whose record extending over
hundreds of years might be disrupted by a single storm event.
Additionally, wave base is perhaps an unreliable criterion on which to
establish the maximum depth of such basins, established on the
occurrence of sand ripples, rip-up clasts, and scour marks now
preserved in the KCF. Sediment structures indicative of bottom-
current activity in the KCF (Wignall, 1989) are observed at virtually all
depths in the ocean today. Komar et al. (1972) discussed surface wave
induced sediment transport to depths slightly exceeding 200 m depth.
Southard and Cacchoine (1972) demonstrated that breaking internal
waves at shelf-break and upper-slope depths can suspend sediment
that might then be transported by bottom currents laterally and to
greater depths. Along the Blake Plateau at 775 m depth, phosphate
83
and ferromanganese concretions are associated with rippled sand
(Manheim et al., 1980). Seafloor erosion in the deep ocean has been
reported at many locations from sediment cores, seismic studies, and
bottom photographs (Johnson 1972; Kennett and Watkins, 1975;
Ellwood and Ledbetter, 1979; Berger and Johnson, 1976). As an
example, relatively stiff Miocene sediment that hosts haloed burrows
filled with Quaternary sediment is now exposed at the surface in the
central Pacific Ocean at greater than 5000 m depth. The burrows,
which have a strong horizontal component, are truncated at the
seafloor (Piper et al., 1986, Fig. 4), requiring relatively recent sediment
scour and presumably redeposition of the Miocene sediment, possibly
as rip-up clasts.
In the calculations that follow, we have assumed a depth of 300 m
for the Kimmeridge Sea; the uppermost 50 m of the water column
being oxic and the lower 250 m being O2 depleted, suboxic or anoxic
for most of the time. A depth greater than roughly 300 m seems
unnecessary for the importation of nutrient-enriched seawater at
depth that supported primary productivity in the photic zone, as open-
ocean seawater is enriched in nutrients at depths as shallow as 100–
200 m (Fig. 4). A shallower depth than 150 m seems equally unlikely,
because the benthic ecological evidence (Oschmann, 1988a,b; Wignall,
1990) and the geochemical results presented here suggesting that
conditions of extreme O2 depletion in the bottom water were
maintained for extended periods of time. This is not to suggest that
the depth remained constant throughout the history of deposition at
any one location, or that it was uniform throughout the basin at any
one time.
Herbin et al. (1995) assigned a period of deposition for the ORIs of
500,000 years. They proposed that the 50 cm thick primary cycles
nested within the ORIs accumulated over a 25,000 year period. On this
basis, the thicknesses of the three primary cycles sampled by
Tribovillard et al. (2005) and examined here of 60, 105, and 120 cm
suggest a somewhat longer duration. Other analyses of sediment
cyclicity from the Wessex Basin suggest several different cycle lengths
(Oschmann, 1988a,b). Weedon et al. (2004) reported a dominant cycle
of 38,000 years, which is close to the Milankovitch obliquity cycle of
41,000 years. This period is based more strongly on the measured
photoelectric factor than on Corg content as reported by Herbin et al.
(1995). House (1985) also reported a cyclicity of 41,000 years for the
upper part of the KCF. We take this as the cyclical duration of the
primary cycles in the Cleveland Basin.
Assuming a complete sediment section in the Cleveland Basin,
sediment thicknesses of the ORIs yield a compacted sediment
accumulation rate of ca. 0.0034 ± 0.0006 cm yr− 1. The primary cycles
had sediment accumulation rates ranging from 0.0015 (ORI 2-2) to
0.0026 cm yr− 1 (OPI 2-1) and the formation as a whole had an
accumulation rate of 0.0036 cm yr− 1 (Eq. (1)). The differences in
accumulation rates between the primary cycles, the ORIs, and the
entire KCF are likely due to a combination of variable dilution of the
marine fractions by the lithogenous fraction and variable accumula-
tion of organic matter. For example, a single sample in primary cycle
ORI 2-2 has a Corg concentration of 31.4%, i.e., the highest accumulation
rate of organic matter or lowest dilution factor, and lowest bulk-
sediment accumulation rate.
A bulk rock density of 2.3 g cm− 3 (Weedon et al., 2004) yields mass
sediment accumulation rates of 35 and 60 g m− 2 yr− 1 for the two
primary cycles and 78 g m− 2 yr− 1 for the ORIs. The density of the
sediment at the time of deposition was likely close to 0.3 g cm− 3, the
approximate density of surface sediment in the Black Sea (Calvert et al.,
1991) and the Cariaco Basin (Piper and Dean, 2002), giving sedimenta-
tion rates prior to compaction of 12, 20, and 26 cm per 103 years,
respectively. The estimates of mass accumulation rates allow the
accumulation rates of Corg and trace elements and the dilution of the
marine fraction by the lithogenous fraction to be determined, but only
over an extended period of time. Even a single sample, as we noted
earlier (Eq. (1)), encompasses as much as 280 years.
84 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
The Cap de la Crèche outcrop, located at the margin of the
Boulonnais Basin, comprises proximal facies (Fig. 2), including cross-
bedded sand bodies (Herbin et al., 1995; Wignall et al., 1996;
Tribovillard et al., 2005), suggesting much shallower depths of
deposition than in the Cleveland Basin. The lithology of these units
reflects a dynamic water column that may have resulted in the
removal of an indeterminate amount of sediment via seafloor
reworking and erosion, such that outcrops may retain an incomplete
sediment record. The enrichment of Zr relative to Al2O3 over the ratio
for WSA (Fig. 8) further suggests the presence of coarse-grained
sediment in the Boulonnais Basin, Zr being present as the heavy
mineral zircon, which is concentrated in coarser-grained sediments
due to the hydraulic equivalence between silt-sized zircon and sand-
sized quartz (Calvert and Pedersen, 2007). The sediments are
probably depleted in Corg, relative to primary productivity, and
enriched in heavy minerals and quartz, compared with the model
lithogenous composition.
The Argiles de Chatillon section (Fig. 2), which Wignall and
Newton (2001) characterize as a transgressive near shore facies
versus the maximum flooding facies of the Corg enriched units in the
KCF (Tyson, 1996), is composed largely of dark marlstones and paper
shales, with as much as 7.5% Corg (Tribovillard et al., 2001). Wignall
and Newton (2001) conclude that it is perhaps the only section in the
Boulonnais Basin that is environmentally correlative with the KCF.
4.2. Lithogenous- and marine-sediment fractions: A trace-element
partitioning model
The composition of the lithogenous fraction of the Cleveland Basin
KCF varies only slightly from the composition of crustal rock
standards, just as the standards themselves vary to a minor degree
(Wedepohl et al., 1969–1978; Gromet et al., 1984; Taylor and
McLennan, 1985; Condie, 1992). For example, the Al2O3 versus Th
relationship in the KCF, both elements being strongly partitioned into
the lithogenous fraction, exhibits a highly significant linear regression
that extrapolates essentially to the origin and has a slope that closely
approaches the Th:Al2O3 ratio in WSA (Fig. 5). We have no
explanation for the seemingly anomalously high Al2O3 concentrations
in OPI 2-1 and no way of evaluating the offset from the other units,
having no measurements of other elements that are partitioned
equally strongly in the lithogenous fraction. However, the samples
from all other units define a single trend.
The ORIs, with a mean concentration of Th of 9.4 ppm (Table 1) and
bulk-sediment accumulation rate of 78 g m− 2 yr− 1, versus 83 g m− 2
Fig. 8. The relationship between Al2O3 and Zr in samples from the Boulonnais Basin site.
Analyses of samples from the Yorkshire cores were not available. The caption to Fig. 6
lists the abbreviations of standards.
yr− 1 for the entire formation (Eq. (1)), yields the following estimate
for the accumulation rate of the lithogenous fraction alone:
Lithogenous faction accumulation rate


−2 −1
= 78 g m yr × ð9:4 ppm ThORI
16 ppm ThKCFmax: Þ
−2 −1
= 46 g m yr ; ð25Þ
representing an average of 60% of the bulk sediment. The maximum
Th concentration in the KCF is 16 ppm (Fig. 5). This lithogenous input
is roughly twice its input into the Black Sea (Calvert et al., 1991). The
source of this fraction to the Wessex Basin (Macquaker and
Gawthorpe, 1993) and possibly the Boulonnais Basin was the
London-Brabant Massif, whereas the source for the Cleveland Basin
could have been the Grampian High (Fig. 1).
The plots of Ni, Cu, V, Mo, and Zn versus Al2O3 demonstrate that
curves drawn from the origin through the lowest metal:Al2O3 ratios
have slopes that closely approach the metal:Al2O3 ratios of the WSA
(Fig. 5). The curves are based largely, but not solely, on samples from
the Boulonnais Basin. As noted previously, Cu and Zn ratios with Al2O3
are ca. 60% of the ratio for the WSA. However, their ratios closely
approach those of the UCC standard, which contains 14.3 ppm Cu and
52 ppm Zn (Wedepohl, 1995).
The concentrations of the marine fraction of the trace elements, on
a sample-by-sample basis, are represented by the displacement of
samples above the minimum curves. For Ni, its concentration in the
marine fraction would have been less than 5% lower had the WSA
value for the Ni:Al2O3 ratio been used to calculate marine Ni
concentrations instead of the slope of the minimum-value curve.
The marine contributions of the other trace elements are similarly
determined for each sample.
4.3. Biogenous sediment fraction: Primary productivity and rate of upwelling
Primary productivity is determined from the accumulation rate of
marine Ni, assuming 10% of primary productivity settles out of the
photic zone (Suess, 1980; Pace et al., 1987; Berger et al., 1988; Thunell
et al., 2000) and its Ni concentration is 18 ppm. Excluding the primary
cycle ORI 2-2, which is considered separately below, the average
marine Ni concentration in the ORIs of 54 ppm (Table 1) and the
average bulk-sediment accumulation rate translate into the following
Ni accumulation rate:
Marine Ni accumulation rate
−2 −1 −2 −1
= ½78 × 54cg m yr = 4200 cg Ni m yr : ð26Þ
The Ni accumulation rate equates to the following flux of Corg settling
out of the photic zone, for which the Corg concentration in organic
matter is 36% (Redfield et al., 1963):
h i
Corg settling flux = 4200 cg Ni m
−2
yr
−1 −
× 0:36 g g
18 cg g ½
−

−2 −1
= 84 g Corg m yr : ð27Þ
This yields a primary productivity of 840 g Corg m− 2 yr− 1, with 90% of
the nutrients recycled in the photic zone. This is similar to primary
productivity on the Peru Shelf (Chavez and Barber, 1987) and
somewhat higher than on the Cariaco shelf of 550 g Corg m− 2 yr− 1
(Goñi et al., 2003).
Miller (1990) considered that the productivity of the Kimmeridge
Sea was fairly low on the basis of an estimate of the long-term average
compacted Corg accumulation rate. Tyson (2004) obtained values for
the Wessex Basin of between 40 and 150 g Corg m− 2 yr− 1 and
Tribovillard et al. (2001) estimated primary productivity in the range
of 52 to 175 g Corg m−2 yr−1 for the Argiles de Chatillon section in
the Boulonnais Basin. Using a high resolution cyclostratigraphic
estimate of the sedimentation rate of the KCF in the Wessex Basin,
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 85

Table 1
Summmary of the composition of sedimentary units examined in this study, from the KCF (Cleveland Basin in Yorksire, England), and age correlative units in Northern France
(Boulonnais Basin). All elemental concentration are in ppm; Corg is given in percent. Data were not available where none are listed.

Basin-interval Ammonite zone Th Cu Marine Ni Marine V Marine Mo Marine Corg Comments

(no. of samples) Cu Ni V Mo
Organic-rich intervals
Cleveland Basin-ORI 5 (6) Pectinatus/Hudlesstoni 8 48 38 86.3 59.7 89.4 6.5 25.0 26.9 8.2 Flixton core, depth 171 to 185 m
Cleveland Basin-ORI 4/3 (6) Hudlesstoni 8 48 38 88.0 62.6 118.7 45.6 32.6 31.6 9.5 Ebberston core, cycle 3,
depth 192.5 to 193.2 ma
Cleveland Basin-ORI 4 (6) Hudlesstoni/Wheatleyensis 10 54 40 81.8 46.4 135.7 44.0 18.0 16.4 9.1 Flixton core, depth 190 to 205 m
Cleveland Basin-ORI 3 (10) Elegans 10 49 35 66.5 30.7 124.4 32.4 11.9 10.2 6.7 Flixton core, depth 212 to 234 m
Cleveland Basin-ORI 2 (11) Autissiodorensis/Eudoxus 9 51 38 92.4 59.5 201.0 107.2 67.0 65.5 6.2 Flixton core, depth 252 to 268 m
Cleveland Basin-ORI 2/2 (16) Eudoxus 11 84 72 158.4 127.3 368.2 278.3 119.3 117.5 13.9 Marton core, cycle 2,
depth 260 to 260.6 ma
Cleveland Basin-ORI 1 (6) Eudoxus 10 66 50 112.0 72.4 166.8 53.9 71.0 68.3 7.1 Flixton core, depth 274 to 290 m

Organic-poor intervals
Cleveland Basin-OPI 5 (0) Hudlestoni Flixton core, depth 185 to 190 m
Cleveland Basin-OPI 4 (1) Scitulus 14 38 19 58.0 7.7 164.0 20.3 3.0 1.0 2.3 Flixton core, depth 205 to 212 m
Cleveland Basin-OPI 3 (3) Autissiodorensis 11 41 26 65.7 25.2 134.7 18.2 6.7 5.4 3.7 Flixton core, depth 234 to 252 m
Cleveland Basin-OPI 2 (0) Eudoxus Flixton core, depth 268 to 274 m
Cleveland Basin-OPI 2/1 (23) Eudoxus 10 71 50 104.2 50.7 165.5 23.3 5.6 4.8 5.7 Marton core, cycle 1,
depth 270 to 270.85a
Cleveland Basin-OPI 1 (5) Eudoxus/Mutabilis 13 41 24 65.2 14.7 164.2 41.0 12.0 10.3 (2.5)b 3.1 Flixton core, depth 290 to 350 m

Organic-rich, organic-poor intervals undifferentiated

Boulonnais Basin-(15) Elegans to Eudoxus 9 20 11 45 19 81 2.8 2.3 1 Argiles de Chatillon
Boulonnais Basin-(11) Pallassioides 7 12 4 28.8 5.9 73.4 4.2 0.5 1 Argiles de Wimereux
Boulonnais Basin-(21) Pallassioides to Eudoxus 8 14 4 39.1 11.2 78.5 3.4 1.5 1 1.9 Cap de la Creche, 102 m outcrop
a
Depths listed for samples collected from the Marton and Ebberston cores (primary cycles 1, 2, and 3) have been scaled to approximate depths within the Flixton core, as reported
in Tribovillard et al. (2005).
b
The marine Mo value of 10.3 ppm is skewed by a single value of 45 ppm; the mean otherwise is 2.5 ppm.

Weedon et al. (2004) obtained a long-term mean primary productiv-
ity for the Kimmeridge Sea of ca. 200 g Corg m− 2 yr− 1, with a range
from b50 to 840 g Corg m− 2 yr− 1. The highest values of ca. 700 to 840 g
Corg m− 2 yr− 1 were from the same ammonite zones as the ORIs in the
Cleveland Basin, consistent with our estimate of primary productivity
for the ORIs based on a completely different approach.
The estimates by Tribovillard et al. (2001) and Tyson (2004) were
based on the calculated burial flux of organic carbon from the linear
sedimentation rate and the pre-compacted bulk density of the rock
and the losses of carbon during recycling and settling through the
water column and on the seafloor. They are significantly lower than
the rates of primary production on modern continental shelves
(Walsh, 1981, 1991; Müller-Karger et al., 2005). Rather, they are
characteristic of primary productivity in the central gyres of the open
ocean (Berger et al., 1988; Behrenfeld and Falkowski, 1997). Under
such low levels of primary productivity, the photic zone extends to as
much as 200 m depth. A seafloor depth less 200 m in the Kimmeridge
Sea would have placed the entire water column of the Wessex and
Boulonnais Basins in the photic zone. Primary productivity would
have extended to the seafloor, offering the opportunity for a highly
efficient utilization of nutrients, as well as high benthic production
(Jahnke et al., 2000, 2008). It seems unlikely that these low levels of
primary productivity would have been maintained under such
conditions. Focusing of sedimented organic matter (Tyson 1996)
would make our calculation of primary productivity a maximum
value. However, it is unlikely that the high level of primary
productivity estimated for the Cleveland Basin can be attributed
totally to focusing, as the accumulation of marine Ni yields the same
high level of primary productivity for the ORIs in the Cleveland Basin
as was obtained by Weedon et al. (2004) for the ORIs in the Wessex
Basin.
Further insight into the production, settling, and burial fluxes of
organic matter in the Cleveland Basin can be obtained from an
estimate of the accumulation rate of Corg in the ORIs, the product of
the bulk-sediment accumulation rate and the Corg concentration
(mean = 8.7 wt.%).
−2 −1 −2 −1
Corg accumulation rate = ð78 × 0:087Þg m yr = 6:8 g m yr ;
ð28Þ
This yields a burial efficiency of 0.81% of primary productivity. The
burial efficiency of Corg estimated by Tribovillard et al. (2001) was 5 to
8%. It has been commonly assumed that such high burial efficiencies
occurred under anoxic bottom waters, but the near total lack of
accumulation of marine V and Mo in the Argiles de Chatillon section
suggests that the bottom water was oxic (see Section 4.4). The burial
efficiency estimated from the level of primary productivity calculated
by Tyson (2004) for the Wessex Basin likely would have been higher.
The variable composition and bulk-sediment accumulation rates of
the rocks, together with uncertainties introduced by our assumptions
of single (model) compositions for the lithogenous fraction and
organic matter, again permit calculations only of mean rates of
primary productivity for the ORIs. Calculations based on the
composition of individual samples are further limited by the sampling
scheme; namely, 1 cm samples taken at ca. 1 to 3 m intervals
(Tribovillard et al., 2005), versus cyclical changes in the geochemistry
of the formation commonly on a decimeter scale (Tyson, 1996). This
has been overcome, but still only partially, by the sampling of two
primary cycles on a 1 to 2 cm interval (see Section 4.5).
The settling flux of organic carbon in the Cariaco Basin, collected by
sediment traps moored 145 m above the basin floor at 1400 m depth,
is 1 to 2% of primary production (Thunell et al., 2000; Goñi et al.,
2003), similar to values reported for the oxic environment of the open
ocean (Pace et al., 1987). One half of this settling flux is buried; the
bulk of the other one half is oxidized at the seafloor, yielding a similar
burial efficiency to that estimated for the KCF. Canfield (1989)
calculated a similar burial efficiency for the Baltic Sea, at a depth of
86 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96

230 m and sediment accumulation rate of 0.023 cm yr− 1. The

sedimentation rate for the ORIs adjusted for compaction was 0.024 cm
yr− 1.
The burial efficiency of Corg in the Cariaco Basin, Black Sea, and
Baltic Sea, and at additional sites in oxic environments in the modern
ocean (Henrichs and Reebugh, 1987) can be summarized by the
compilation of carbon accumulation rates and the linear sedimenta-
tion rate (Fig. 9) for a wide range of depths and redox conditions
(Calvert et al., 1991). The data from the KCF lie close to the curve
presented in this figure, revealing that Corg preservation was not
enhanced in the Kimmeridge shales compared with its preservation in
modern marine sediments. The use of logarithmic axes in Fig. 9
naturally obscures a good deal of scatter in the data, but is useful as a
representation of several orders of magnitude with fixed relative
precision (Dehaene et al., 2008).
It is likely that local rivers delivered a small fraction of the nutrient Fig. 10. Relationship between marine Ni versus Corg. All samples are enriched in Ni,
demand of phytoplankton in the Kimmeridge Sea. An estimate of the relative to its concentration in marine plankton, shown by an asterisk (Collier and
area extending some 3000 km from the Barents Sea to the English Edmond, 1983). Sample symbols are listed in Fig. 5.
Channel would have been greater than 5 × 105 km2 (Oschmann, 1990).
If the mean level of primary productivity for the entire sea was only
half the level estimated from the Yorkshire core, primary productivity
would have been 2 × 1014 g Corg yr− 1, on average. The NO− 3 demand The Cumarine:Nimarine ratio is 0.56 (7.5 ± 1.4 ppm:13.4 ± 2.4 ppm),
would have been 2 × 1018 μmol NO− 3 yr
−1
using the mean C/N ratio of which is similar to the average ratio for plankton of 11:18, or 0.61
marine phytoplankton in Section 3.2.1. This demand would have (Collier and Edmond, 1983). The similarity of the ratios identifies a
required a fluvial input 380 times the fluvial input to the Black Sea single marine biogenous source for both elements and probable lack
(Eq. (11)), or more than 20 Amazon Rivers at its current NO− 3 of anoxic conditions in the Boulonnais Basin (see Section 4.4), which
concentration and discharge rate (Maybeck, 1982). would have led to an enrichment of Cu relative to Ni due to the
The relationship between Ni and Corg lends support to our additional trapping of Cu from anoxic bottom waters where Ni
contention that Ni can be used as a proxy for Corg deposition. The removal does not occur (Piper and Dean, 2002). The similarity of the
mean Corg:Nimarine ratio in the ORIs is 0.0019 g μg− 1 (Fig. 10). Although Cumarine:Nimarine ratio in the Argiles de Chatillon section to that of
exhibiting considerable scatter, it is similar to the ratios in sediment modern plankton further supports the model compositions of both
from both the Black Sea and Cariaco Basin of 0.0012 and 0.0013 g μg− 1, Jurassic plankton and the lithogenous fraction.
respectively. The higher ratio for plankton of 0.020 μg g− 1 (Collier and Importation of open-ocean seawater, necessary to support primary
Edmond, 1983; Eq. (27)) merely reflects the loss of Corg via its productivity, may have been restricted by the presence of islands and
oxidation in the water column and on the seafloor during burial shallow shelves in, and marginal to, the Kimmeridge Sea (Ziegler,
(Eq. (28)). 1990). However, the presence of a complex seaway between the
Added support for this method of estimating organic matter Arctic, Central Atlantic and Tethyan Oceans (Oschmann, 1990;
accumulation is provided by the relationship between Cu and Ni in the Bjerrum et al., 2001) would have allowed for free exchange of
marine fraction of sediment from the Argiles de Chatillon section, seawater between the Late Jurassic epeiric sea and the Arctic Ocean
which, as noted earlier, is perhaps the only sediment section in the and/or the newly opened Atlantic Ocean. It is possible that the islands
Boulonnais Basin that can be compared with the KCF in England and shoals actually enhanced primary productivity in the Kimmeridge
(Wignall and Newton, 2001). The Cumarine versus Nimarine trend of the Sea by disrupting the flow field of surface currents and enhancing
two trace nutrients at this site (Fig. 11) exhibits a regression with shallow upwelling in a manner similar to the enhancement of
r2 = 0.57, which increases to 0.77 with the omission of a single sample. production in the lee of submarine banks and oceanic islands today,

Fig. 9. The relationship between the accumulation rate of Corg and bulk sedimentation
rates of modern basins. The curve is based on sediment samples from the open ocean
(Calvert et al., 1991).
Fig. 11. Marine Cu versus Ni in samples from the Boulonnais Basin. The slope of the
curve represents the mean ratio in marine plankton (Collier and Edmond, 1983).
Concentrations less than 5 ppm should be disregarded, owing to the uncertainty
imposed from modeling the elemental composition of the lithogenic versus marine
fractions (Fig. 5).
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
the so-called Island Mass Effect (Doty and Oguri, 1956; Heywood et al.,
1990; Perissinotto et al., 1992).
The vast extent of high levels of primary productivity is similar to
its distribution in the ocean today (Behrenfeld and Falkowski, 1997).
In the northern Indian Ocean, primary productivity seasonally extends
oceanward from the upwelling center along the Arabian Peninsula
several 100 km south and east towards the center of the Arabian Sea
(Brock and McClain, 1992; Ryabchenko et al., 1998; Dickson et al.,
2001; Wiggert et al., 2005). In the Atlantic Ocean, it extends an even
greater distance from centers of coastal upwelling along northwest
(Huntsman and Barber, 1977; Barber and Smith, 1981) and southwest
Africa (Nelson and Hutchings, 1983; Pitcher et al., 1992) and off Peru in
the Pacific Ocean (Brink et al., 1981). In the North Atlantic elevated
levels of primary productivity extend from east and south of Iceland
into the Norwegian Sea and North Sea, being highest in coastal areas
of Ireland and Great Britain (Taylor et al., 1993; Stenseth et al., 2004). It
is seasonally elevated also throughout several inland seas, e.g., the
Gulf of California (Hidalgo Gonzalez and Alvarez Borrego, 2004;
Douglas et al., 2007), the East China Sea (Gong et al., 2003), Yellow Sea
(Behrenfeld and Falkowski, 1997), and the Sea of Okhotsk (Sorokin,
1999). It is similarly high in the Baltic Sea, but anthropogenic nutrient
inputs into this and the other ocean margin seas limit this comparison.
The elevated levels of primary productivity that are characteristic of
these and other ocean margins require the importation of nutrients
into the photic zone from depths of a few tens to ca. 200 m.
The elevated sea level in the Late Jurassic that flooded vast areas of
northern and western Europe (Ziegler, 1990; Blakey, 2001; Scotese,
2001) probably contributed to the importation of nutrient-enriched
seawater at depth from the open ocean. Haq (1987) has estimated a
sea level rise of 150 m. Studies of the Russian Platform (Sahagian
et al., 1996) place the rise at 50 m, although more recent work has
questioned the way in which past sea levels have been determined
(Moucha et al., 2008). Regardless, the increase in sea level likely
established a connection between the Kimmeridge Sea and the global
ocean. A connection to the open ocean only 150–200 m deep would
have routed major ocean-boundary currents onto the continent.
These currents today—the Gulf Stream, Canary Current, Benguela
Current, Agulhus Current, Peru Current, California Current, Kuroshio
Current—are restricted to the margins of the ocean basins (Sverdrup
et al., 1942). Together with the equatorial upwelling systems, they
account for 75% of global ocean primary productivity (Chavez and
Toggweiler, 1995). Their incursion onto the continents in Late Jurassic
time would have transferred into epeiric seas the enormous
inventory of nutrients they transport between ca. 100 and 300 m
depth. This importation of nutrients would have supported high
primary productivity at sites in the Kimmeridge Sea, West Siberian
Basin, and other epeiric seas. The sea-level rise of only 50 m would
also have enhanced trapping of terrigenous sediment in river
estuaries, limiting dilution by the accumulating lithogenous material
(Eq. (25)). Sea level reached a maximum during deposition of ORI-4,
but a high-stand may have been maintained throughout deposition
of all of the ORIs (Miller et al., 2005), owing to seafloor subsidence in
response to crustal rifting (Ziegler, 1990; Graversen, 2002), as well as
eustatic sea-level rise.
The importance of upwelling zones for the deposition of petroleum
source beds, an idea that dates back to Trask (1932), was examined by
Parrish (1987) using global paleoclimate models and the distribution
of rock lithologies. Although the boundary conditions used by Parrish
have been questioned by Tyson (1995), Parrish found statistically
significant numbers of co-occurrences of organic-rich facies and
predicted sites of upwelling zones for much of the Phanerozoic but the
correspondence was not uniform. Notably, there was no link between
the formation of organic-rich facies and proposed upwelling zones for
the Late Jurassic. One possible explanation for the failure of a
correlation may have been the transfer of major nutrient reservoirs
onto the continents, as proposed here, owing to the sea-level rise. The
87
shallowness of these epeiric seas would have facilitated mixing of this
high nutrient bottom water into the photic zone, such that many sites
of elevated primary productivity would have been located in epeiric
seas and not along the ocean margins, as is their location today.
4.4. Hydrogenous sediment fraction: water-column redox and residence
time
We have shown that dissolved V and Mo are removed from the
anoxic bottom waters and deposited in the sediments of the Cariaco
Basin and the Black Sea, with V removal at a higher redox potential
than Mo. This difference allows the V versus Mo enrichment in
sediments above their lithogenous contributions to identify past
conditions of suboxia (V) and anoxia (V and Mo) in the KCF
sedimentary sequences. The much higher marine V:Mo ratios versus
the concentration of marine Mo in the Cleveland Basin section
(Fig. 12), compared with their values in the sediments in the Black Sea
and Cariaco Basin that are accumulating under fully anoxic conditions,
suggest that the bottom waters in the Cleveland Basin varied from
suboxic to anoxic during deposition of the ORIs, possibly achieving
oxic conditions for brief periods of time, and from oxic to suboxic
during deposition of the OPIs. For most of the depositional history,
bottom-water conditions were suboxic. The high concentrations and
accumulation rates of marine Mo (100 to 200 ppm) and marine V (200
to 300 ppm) in many samples from the ORIs further suggest free
exchange of bottom water with the open ocean. Unlike the major
Fig. 12. The relationship between Mo and V:Mo ratios in the marine sediment fraction of
the KCF. See Fig. 2 for the location of the OPIs and ORIs in the KCF. See Fig. 5 for the
identification of sample symbols. Colors define the different bottom-water redox
conditions as labeled. For the purpose of constructing this diagram, i.e., to show all values
as positive, marine Mo and V concentrations that are less than 2 times the detection limit
(1 ppm) are assumed to be 1 ppm. All marine V:Mo ratios less than 0.5 are set at 0.5.
Samples with Mo concentrations less than approximately 10 ppm have a V:Mo ratio
between 0.5 and 100. Most of these samples are from the OPIs. Such ratios suggest
deposition under oxic to suboxic conditions. An oxic area that includes these samples is
included for illustrative purposes only, as hydrogenous V and Mo concentrations would be
zero in sediment deposited under oxic redox conditions, although the two should have a
weak biogenic input. Samples with a marine Mo fraction greater than 15 ppm define the
anoxic region and the suboxic-to-anoxic region. A suite of samples from a single outcrop
typically plots along a single concave-up curve defined by decreasing V:Mo ratios with
increasing Mo concentrations. This distribution is seen for the Permian Phosphoria
Formation (Piper et al., 2007) and the Devonian–Mississippian Ohio-Sunbury Shale of the
Appalachian Basin (Perkins et al., 2008). The trend identifies samples deposited under
anoxic conditions as having V:Mo ratios approaching that of seawater, whereas samples
deposited under suboxic conditions have elevated V:Mo ratios, owing to the different redox
conditions under which the two accumulate (Emerson and Huested, 1991).
88 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
nutrients, which are recycled within the photic zone, the accumula-
tion of these redox-sensitive trace elements from bottom water and
the trace nutrient Ni from the photic zone would have required
continuous renewal of bottom waters to support their flux to the
seafloor. Any barrier that might have restricted advection of water into
the Kimmeridge Sea was likely no shallower than the sill to the Cariaco
Basin. If shallower, their concentrations and accumulation rates would
have approached values now observed in the Black Sea. There may
have been no sill at all, similar to the bathymetry of the Gulf of
California, as the exchange of bottom water with the open ocean was
more dynamic (Eq. (29)) than in either the Black Sea or Cariaco Basin,
and primary productivity (Eq. (27)) was significantly higher. The
prevalent suboxic–anoxic condition of the Kimmeridge bottom waters
with occasional oxic periods is consistent with the dysaerobic benthic
faunal evidence of Oschmann (1988a,b) and Wignall (1990), as well as
the range of the Indicator of Anoxicity developed by Raiswell et al.
(2001), whose values are consistent with the assignments of the
oxygen-restricted biofacies identified by Wignall and Hallam (1991).
As the lower part of the water column in the Cleveland Basin was
largely suboxic to anoxic throughout deposition of the ORIs, the
bottom-water RT should be given by the inventory of V in the water
column and its rate of accumulation on the seafloor. If we assume a V
concentration in seawater of 1.8 ppb (Collier, 1984) and its removal
from strongly O2 depleted bottom water of about 10% (Emerson and
Huested, 1991; Piper and Dean, 2002), the average V concentration in
the marine fraction of the ORIs of 80 ppm gives the following mean RT:
h i
3 −2 −1
RT = 250 × 10 L m × 1:8 cg V L × 0:075
h i
−2 −1 −1

78 g m yr × 80 cg g = 5:4 yr: ð29Þ
The efficiency of V removal from the bottom water of the
Kimmeridge Sea under the suboxic to anoxic conditions is, of course,
not constrained, but for the purposes of this analysis we have taken
what may be a conservative value of ca. one fifth its removal from the
bottom waters in the Cariaco Basin (Emerson and Huested, 1991).
Likewise, the concentration of V in Jurassic seawater could have varied
from its concentration in the ocean today. Finally, selecting a seafloor
depth of 200 m rather than 300 m reduces the RT to 3.2 years, which
still would have precluded seasonal overturns.
Wignall (1989, 1994) presents evidence of flushing events in the
Kimmerdige Sea by oxic seawater, possibly lasting several years
separated by periods during which the bottom water was suboxic to
anoxic. Although flushing events more or less continuously on the
scale of seasons seems unlikely, the low mean sediment accumulation
rate of 0.0034 cm yr− 1 and bottom-water RT of a few years for the
ORIs can account for the presence of epifauna coexisting with textural
and geochemical signals of extreme O2-depleted, even anoxic,
conditions. Bottom-water flushing events likely were more prevalent
during deposition of the OPIs, leading to oxic bottom waters that may
have persisted over centuries. None of these rules out the possibility of
storm conditions that might have briefly interrupted suboxic to anoxic
conditions, even in the ORIs.
The marine V and Mo values of samples from the Argiles de
Chatillon site in the Boulonnais Basin plot in the oxic to oxic-suboxic
field (Fig. 12); marine V and Mo concentrations are essentially zero in
most samples (Table 1). Although their low concentrations might be
explained by a limited volume of suboxic to anoxic water in this
shallow marginal setting (Wignall and Newton, 2001), the near total
absence of Mo, which can accumulate weakly from seawater on open
continental shelves under suboxic conditions (McManus et al., 2006),
supports dominantly oxic bottom-water conditions in the Boulonnais
Basin. The similarity of the Cu:Ni ratio in the marine fraction (Fig. 11)
to the ratio in plankton (Collier and Edmond, 1983) also supports oxic
to suboxic bottom-water conditions, where the accumulation of Cu
under anoxic conditions (Jacobs et al., 1985, 1987) would have
elevated the Cu:Ni ratio in the marine-sediment fraction, relative to
the ratio in plankton.
Sulfidic conditions within the shallow sediment horizons and
extending into the bottom water likely created ideal conditions for
organic matter preservation via sulfurization (Sinninghe Damsté and
de Leeuw, 1990; Lallier-Vergès et al., 1997; van Dongen et al., 2006)
and the hydrogenation of biomolecules by H2S (Hebting et al., 2006).
This draws attention to the care that is needed when using
sedimentary proxies of anoxia to distinguish between the chemical
state in the pore water of accumulating sediments and that of the
water column. In relatively shallow-water marginal marine settings
today, the sediment pore water is commonly anoxic, whereas the
bottom water is only occasionally anoxic, likely similar to the
condition in the Kimmeridge Sea, where the bottom water was
dominantly suboxic (or dysaerobic; Wignall, 1991).
4.5. Hydrography of primary cycles
The detailed sampling of two primary cycles, one in OPI 2 (OPI 2-1)
and one in ORI 2 (ORI 2-2), offers the opportunity to compare the
hydrography of the water columns of these two apparently different
environments of deposition (Fig. 13). A relatively uniform rate of
flushing of bottom water during deposition of the primary cycle ORI
(2-2) is suggested by the concentration of marine V. In the 16 samples
that were collected from this cycle, marine V averages 270 ppm
(Tribovillard et al., 2005) and varies over the rather narrow range of
195 to 320 ppm. Bottom-water RT varied from 4.0 to 6.6 years
(Eq. (29)), assuming a linear rate of sediment accumulation. Marine
Mo varies between 25 and 220 ppm and the V:Mo ratio varies from
0.84 to 54, with a single high value at the very top of the section
(Fig. 13). Omitting this one value, the ratio averages 3.3 ± 2.7. The
trend of the ratios, lower in the center of the unit than at the top and
bottom, are indicative of a gradual change in bottom-water redox. The
higher ratios at the top and bottom are indicative of bottom water
suboxia at these times (V:Mo ratios greater than ca. 3), whereas the
bottom water was strongly anoxic throughout deposition of the
middle part of the section. The high Corg and Ni concentrations in the
middle of the section suggest that primary productivity was a major
factor in varying the redox conditions.
Calculations of primary productivity (Eqs. (26) and (27)), based on
the concentration of marine Ni of 120 ± 55 ppm, averaged 840 ± 380 g
Corg m− 2 yr− 1. The upper limit exceeds measured values in the oceans
today by ca. 45%. A 2.7-fold increase in Th from the center of the cycle
to the margins suggests that the high Ni concentration in the central
part of the cycle may reflect in part lower dilution of the marine
fraction by the lithogenous fraction than at the top and bottom of the
cycle. Marine V also exhibits slightly lower concentrations in this
interval.
The chemical composition of a primary cycle within OPI 2 (OPI 2-1)
was also determined on a centimeter scale (Tribovillard et al., 2005).
The concentration of marine V is less that 5 ppm in 12 of the 23
samples (Fig. 13). The marine Mo concentration varies from less than
1 ppm to 35 ppm, but is less than 3 ppm in 8 of the same samples
(Fig. 13). The concentrations of both metals in these samples are
simply below the limit of the modeling scheme. Within the center of
the cycle, the marine V:Mo ratios are elevated, owing to V en-
richment. This trend suggests that the bottom water varied from oxic
toward the top and bottom of the cycle (low concentrations of both
elements) to suboxic in the center (elevated marine V:Mo ratios).
Water column chemistry was significantly less stable than during
deposition of ORI 2-2. Similar to ORI 2-2, marine Ni and Corg are
elevated in the center of the cycle. The average marine Ni
concentration of 40 ± 37 ppm corresponds to a primary productivity
of 480 ± 440 g m− 2 yr− 1, significantly lower than primary produc-
tivity of the ORIs. The results of the analyses of these two primary
 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96 89

Fig. 13. Relationship between Corg, marine Ni concentrations, and the marine V:Mo ratio in two primary cycles, one from ORI 2 and one from OPI 2. A third primary cycle (ORI 4-3) has
a thickness greater than 120 cm. It was sampled only sparingly (Table 1), but trends in its geochemistry parallel those in ORI 2-2. The main difference between the two is lower
concentrations of Corg, Mo, Ni, and V in ORI 4-3 than in ORI 2-2; in both primary cycles, half of the samples have a V:Mo ratio less than 2. The individual cycles are interpreted as
accumulating over 41,000 years (see text). In OPI 2-1, the filled diamonds represent samples in which the marine V concentration is less than 5 ppm and the marine Mo concentration
is less than 2 ppm; their concentrations are less than the modeling scheme is able to calculate. These samples likely accumulated under oxic conditions. Alternatively, their low
marine concentrations may reflect dilution by the lithogenic fraction. The filled squares represent samples for which marine Ni is less than 5 ppm. Note the two x-axes. Greater scatter
to the data for the OPI 2-1 than for the ORI 2-2 suggests less stable water column conditions in the former. In both units, but more so for the primary cycle ORI 2-2 (and ORI 4-3), both
Ni and Corg track V:Mo ratios, suggesting that primary productivity was the major factor that controlled the concentration of Corg and bottom-water redox, in the former case more so
than dilution by the lithogenous fraction and in the latter case more so than advection.

cycles support our interpretations of the ORIs that were sampled at
much less frequent intervals.
5. Summary and conclusions
The chemistry and hydrography of the water columns and the
geochemistry of the Holocene sediments of two modern anoxic basins—
the Cariaco Basin and the Black Sea—have been used to model the
processes responsible for the deposition of a group of redox-sensitive
trace metals and trace nutrients in the two basins. By making several
simplifying assumptions, the model has then been applied to hindcast
the hydrography and geochemistry that prevailed during the deposition
of the Late Jurassic Kimmeridge Clay Formation in the Cleveland Basin,
Yorkshire, England. The results reveal that primary productivity in the
basin during deposition of five ORIs was ca. 840 g Corg m− 2 yr− 1, the
same as its rate on the Peru shelf today. The deposit currently has
exceptionally high concentrations of Corg, although less than one percent
of primary productivity escaped oxidation during deposition, burial, and
diagenetic losses. Evocation of high planktonic productivity as the first-
order control of the organic enrichment of the KCF is in accordance with
the conclusions of many workers (Huc et al., 1992; Bertrand et al., 1994;
Ramanampisoa and Disnar, 1994; Tribovillard et al., 1994; Saelen et al.,
2000; Jenkyns et al., 2002; Tribovillard et al., 2005).
To sustain the high level of primary productivity, the basin
required the importation of nutrient-enriched seawater from the
open ocean at a depth below the photic zone no greater than 50–
250 m. Nutrients were delivered to the photic zone by upwelling and
mixing, probably more so in winter and spring than summer and fall,
when a seasonal thermocline would have been weakened by atmo-
spheric cooling. Their mean rate of input suggests that the RT of
bottom water was a few years to decades. Although much lower than
the RT in modern anoxic basins, it suggests seasonal overturns of
bottom water were unlikely.
Accumulations of redox-sensitive trace elements (V and Mo) in the
ORIs recorded O2 depleted conditions that, except for relatively brief
periods when the water column was oxic throughout, extended from
the sediment pore water into the water column itself for extended
periods of time. Although redox conditions varied from oxic to anoxic,
suboxic conditions were the most prevalent, consistent with the
widespread occurrence of dysaerobic biofacies throughout much of
the KCF and the rarity of horizons entirely lacking benthic fossils
(Oschmann, 1988a; Wignall, 1990). Similar to the nutrient demand in
the photic zone, the accumulation of these trace elements required
renewal of bottom water on the scale of a few years. The suboxic state
of the Kimmeridge Sea bottom waters should not be considered rare
or unusual. Denitrifying conditions occur over vast areas of modern
continental margins, e.g., beneath areas of high primary productivity
in the Arabian Sea (Ganeshram et al., 2000), the continental slopes of
the Gulf of California (Calvert, 1964), western Mexico (Codispoti,
1980), the California Borderland basins (Soutar and Crill, 1977), and
continental shelves off Namibia (Bailey, 1991) and Peru (Arthur et al.,
1998). Combinations of high organic carbon fluxes and restricted
ventilation cause these environments to be poised at this suboxic
state. Under this state both NO− 3 (40 μM) and O2 (50 μM) act as
oxidants. There seems no reason why a similarly vast expanse of this
hydrographic condition should not have occurred in the ocean at
relatively shallow depths in the past.
Calculations of the nutrient and trace-metal budgets for the KCF
emphasize the dominant role of the lateral supply of nutrients required
to support the high level of plankton production. Nutrient fluxes from
offshore, rather than atmospheric, groundwater, volcanogenic, or even
fluvial sources, drove primary production, similar to conditions in the
ocean today. Whereas local nutrient fluxes to the photic layer of the
ocean are achieved by vertical mixing and upwelling from shallow sub-
surface depths, these nutrients are transported from high southern
latitudes at sub-thermocline depths throughout the oceans. The
90 D.Z. Piper, S.E. Calvert / Earth-Science Reviews 95 (2009) 63–96
nutrients supplied by this “conveyor” are now and were in Late Jurassic
time ultimately derived from the deep Atlantic and or Arctic, wherein
they accumulated from deep water particle recycling. This process
effectively recycles and re-routes nutrients delivered to the global
ocean from their ultimate sources, such as fluvial inputs from the
continents and from the global atmosphere (Sarmiento and Gruber,
2006). Waters with such nutrient inventories currently flow into the
Cariaco Basin across the shallow sill separating the basin from the deep
Caribbean to the north. In the case of the Black Sea, nutrients and
metals are supplied to the basin in the sub-surface Mediterranean flow
through the Bosporus Strait, which gains nutrients during its passage
through the Aegean Sea and the eastern Mediterranean. Although the
nutrient concentrations in these shallow sub-surface waters are lower
than at abyssal depths of the ocean, they are high enough to dwarf
nutrient supplies from local rivers, owing to the volumes of flow. A
similar mechanism must have operated in the Kimmeridge Sea to
account for the organic enrichment in the KCF, where exceptionally
high levels of primary production extended virtually uninterruptedly
over time periods possibly as long as 41,000 years.
The combined evidence for this advection scheme, together with an
elevated sea level in Late Jurassic, suggests that the deposition of the
KCF occurred during and as a result of a major global flooding event.
Sea level may have reached several tens of meters above present,
attaining its maximum at the beginning of deposition of ORI-4,
although the high-stand may have persisted throughout deposition of
most of the ORIs and the intervening OPIs. Such flooding could have
pushed the major surface currents of the open ocean onto the
continents. Today, these currents are restricted to the continental
margins, where Ekman transport of surface waters away from the
coasts supports high primary productivity. Their incursion onto the
continents in the Late Jurassic would have transferred into epeiric seas
the enormous inventory of nutrients they transport between 50 and
250 m depth and from which upwelling into the photic zone occurs.
The sea level high-stand in Late Jurassic, more so than the actual sea-
level rise itself, thus was a critical factor in the accumulation of Corg
enriched sediments in the Kimmeridge Sea. Flooding of large areas of
low relief in northern and western Europe by as little as a 50 m sea-
level rise would further have resulted in trapping much of the
terrestrial sediment in river estuaries. The persistence of such an
environment at a single site for thousands to several million years
(Herbin et al., 1995) was maintained by the lateral extension of the
environment over tens of thousands to several hundred thousand
square kilometers, from the Barents Sea to the English Channel. Thus,
the oceanographic conditions responsible for the accumulation of the
organic-rich Kimmeridge Clay facies, obtained from the modeling
results at a single core site, are likely representative of this vast area.
Acknowledgements
Nicolas Tribovillard generously provided the chemical data for the
Kimmeridge Clay Formation and reviewed an early draft of the
manuscript. Reviews by James Hein, Walter Dean, Richard Tyson, and
an anonymous reviewer also greatly improved the manuscript.
Support for this research was provided by the Natural Sciences and
Engineering Research Council of Canada (SEC) and the United States
Geological Survey (DZP).
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