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Earth-Science Reviews 86 (2008) 1 – 14

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Orogenesis vs. diagenesis: Can we use organic-rich shales

to interpret the tectonic evolution of a depositional basin?
S.M. Lev a,⁎, J.K. Filer a , P. Tomascak b
a
Towson University Geochemistry Laboratory, Towson University, Towson, MD, USA
b
Department of Earth Sciences, SUNY Oswego, Oswego, NY, USA
Received 9 March 2007; accepted 16 July 2007
Available online 9 August 2007

Abstract

Black shales from the southern Appalachian Basin and the southwest Welsh Basin have anomalous U–Pb and Nd model ages
suggesting syn- and post-depositional resetting of the Sm–Nd and U–Pb isotopic systems. This alteration to the primary detrital
signature of these two shale sequences is indicative of black shale diagenetic/depositional processes that obscure paleo-
environmental and provenance information recorded prior to and during deposition. The trace element and isotopic signatures of
these two shale sequences reveal a syn-/post-depositional history that is de-coupled from the coeval orogenic history of the region
making it difficult to reconstruct the tectonic and oceanographic conditions present at the time of deposition.
Both the Ordovivian Welsh Basin and the Devonian Appalachian Basin sequences host REE- and U-bearing diagenetic
phosphate minerals that play a critical role in the whole rock REE and U budgets. In the Welsh Basin shales, early diagenetic
apatite and a later monazite phase dominate the REE budget and cause the redistribution of REE early in the basin's history (ca.
460 Ma). This redistribution is recorded by the Sm–Nd system (450 ± 90 Ma) and the Nd model ages that are anomalously
old by as much as 20% (TDM N 2.0 Ga). This early history is complicated by a Permo-Triassic fluid event affecting the whole rock
U-budget and resetting the U–Pb isotopic system at 193 ± 45 Ma. The Appalachian Basin sequence appears to have a much less
complicated history yet still records a significant disturbance in both the Sm–Nd isotopic system (392 ± 76 Ma) and the Pb isotopic
system (340 ± 50 Ma) at about the time of deposition (ca. 365 Ma).
These two sequences suggest a pattern of diagenetic disturbance common to black shales. These processes are unique to black
shales and must be considered when interpreting provenance and paleo-environmental information from the black shale sequences.
Although these rocks are susceptible to alteration, the alteration may provide extensive information on the post-depositional history
of the basin while still retaining some primary depositional information. If black shale processes are considered during the
interpretation of isotopic and trace element signatures from organic-rich shales, it may be possible to recover an extensive basin
history.
© 2007 Elsevier B.V. All rights reserved.

Keywords: black shale; provenance; diagenesis; rare earth elements; uranium

⁎ Corresponding author. Department of Physics, Astronomy, and Geosciences, Towson University, 8000 York Road, Towson, MD 21252, USA.
E-mail address: [email protected] (S.M. Lev).

0012-8252/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.earscirev.2007.07.001
2 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14

1. Introduction ages suggesting syn- and post-depositional resetting of the

Sm–Nd and U–Pb isotopic systems. This alteration to the
The geochemistry of marine shales is one of the most primary detrital signature of these two shale sequences is
widely used tools in the study of basin evolution. These indicative of the black shale diagenetic/depositional
sediments can record both the character and age of the processes described previously. The Ordovician and
source rocks to a basin as well as the paleo-oceanographic Devonian shales examined herein document the effects
conditions at the time of deposition. There are however, a of diagenetic overprinting of original indicators of
number of processes that may obfuscate this information provenance and related tectonic information such as the
beginning with chemical weathering and ending with age of source terrane. Despite such overprinting,
metamorphism (McLennan, 1989; McLennan et al., approaches are suggested by which this masked primary
1993). In addition to these perils, organic-rich black information can be recovered.
shales are susceptible to a very specific set of processes
that are particularly effective at redistributing the rare earth 2. Geologic setting
elements (Milodowski and Zalasiewicz, 1991; Bock et al.,
1994; Cullers et al., 1997; Lev et al., 1998, 1999; 2.1. Welsh Basin
McLennan et al., 2003; Kidder et al., 2003; ) and enriching
uranium (Anderson et al., 1989; Barnes and Cochran, Welsh Basin Ordovician black shales from this study
1990; Klinkhammer and Palmer, 1991). were deposited beginning in the Llanvirn through the
REE, which are generally thought to behave conser- lower Caradoc near the Fishguard Volcanic Complex,
vatively in the near surface environments associated with which is characterized as a back-arc tholeiitic sequence
sediment transport and deposition, are commonly redis- (Bevins et al., 1984, 1992) (Fig. 1). This center was
tributed from detrital and syn-depositional phases into active from the Arenig–Llanvirn times based on
diagenetic phases (Elderfield et al., 1985; Elderfield and outcrop relationships with associated shales (Fig. 1).
Sholkovitz, 1987; Milodowski and Zalasiewicz, 1991; During the Llandeilo–Caradoc times active volcanism
Murray et al., 1991; Ohr et al., 1991, 1994; Bock et al., was more prevalent in northern Wales near Snowdonia
1994; Bouch et al., 1995; Cullers et al., 1997; Lev et al., (Kokelaar et al., 1984). The deposition of shales in this
1998, 1999; McLennan et al., 2003; Kidder et al., 2003). study coincided with the closing of the Iapetus Ocean
The significance of this redistribution is two-fold; and were deposited in a back-arc setting dominated by
1) information on the character of the source region and volcanic deposits (Bevins and Roach, 1979; Bevins,
the conditions of deposition are either partially or 1982; Bevins et al., 1984; Kokelaar et al., 1984;
completely lost and, 2) the age of the source area, Woodcock, 1984; Kokelaar, 1988; Traynor, 1988;
available through the Sm–Nd isotope system, is altered. Bevins et al., 1992). The sedimentation age, based on
The uranium content of organic-rich shales will the graptolite biozones and the U–Pb zircon ages from
generally be highly correlated with the total organic the closely associated Llanrian and Longvillian volca-
content of the shale (Lev and Filer, 2004 and references nic beds, is well constrained to between 466 and 455 Ma
therein). This is indicative of the reducing conditions that (Jenkins, 1979; Hughes et al., 1982; Tucker et al., 1990;
develop at or near the sediment water interface during the Harland et al., 1990) (Fig. 1).
deposition of organic-rich facies. These conditions will Previous studies provide some constraints on the
lead to the enrichment of U during deposition and thermal history of these rocks. Metamorphic maps of
diagenesis (Anderson et al., 1989; Barnes and Cochran, Wales, based on Ca–Al silicate assemblages in metaba-
1990; Klinkhammer and Palmer, 1991; Lev et al., 2000; sites and on the distribution of illite crystallinity in shales,
McLennan et al., 2003). This type of U enrichment indicate a regional record of diagenetic to greenschist
process will impact the U–Pb isotope systematics of facies conditions in the Lower Paleozoic rocks of the
the shale being deposited and the Pb isotopic compo- Welsh Basin (Kubler Index Range of 0.23 to 0.46° 2θ;
sition of the shale will no longer reflect the composition Fettes et al., 1985; Robinson and Bevins 1986; Bevins and
of the source area. The U–Pb isotopic system remains Robinson 1988; Roberts et al., 1996). The clays in the
potentially open post-deposition as basin fluids may Llanvirn–Llandeilo–Caradoc shales consist of well-
further alter the U and/or Pb concentration of the ordered illite (R3) and have a Kubler Index Range of
organic-rich deposit. 0.20 to 0.46° 2θ, which is in general agreement with the
Black shales from the Devonian of the southern proposed late diagenetic to epizone temperatures (200–
Appalachian Basin and the Ordovician of southwest 300 °C) recorded by clay mineralogy elsewhere in the
Welsh Basin have anomalous U–Pb ages and Nd model Welsh Basin (Lev, 1994).
 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14
Fig. 1. Location map and general stratigraphic framework of the Llanvirn–Llandeilo black shales from Southwest Wales, U.K. Sample locations are indicated and the 465 Ma age is a U–Pb zircon age
from the Llanrian Volcanic bed within the section (Tucker et al., 1990).

3
4 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14

2.2. Appalachian Basin been interpreted to mark the deeper water transgressive
phase of the probable fourth order eustatic sea level cycles
The Devonian samples in this study are from distal (Filer, 2002). Both nodular concretions as well as one
marine shales deposited in the Appalachian foreland basin continuous bed of siderite are present as well. Most of the
(eastern United States) associated with the Late Devonian samples analyzed for the current study come from the Java
portion of the Acadian orogeny. Unweathered kilogram Formation (Fig. 4). The transition to the overlying lower
sized samples were collected from an exposure in Huron Member equivalents is abrupt, and this unit consists
southwestern Virginia (Fig. 2). The sampled interval is of about 60 m of generally massive dark organic rich
within the lower black shale member of the Chattanooga shale. Only two samples from the very base of the lower
Shale, and, according to a published reference section, is Huron Member were analyzed (Fig. 4).
equivalent to the Java Formation of New York State and Regionally, Devonian and younger strata were sub-
the overlying basal lower Huron Shale Member of the jected to fold and thrust deformation during the Late
Ohio Shale (Fig. 3, Filer et al., 1996). Over (2002) Paleozoic Alleghenian orogeny. The sampled exposure
examined the conodont biostratigraphy of this outcrop. He occurs in the roadcuts near the crest, but on the northwest
placed the boundary between the Frasnian and Famennian flank of the Powell Valley anticline within the Pine Moun-
Stages (364 Ma, Gradstein and Ogg, 1996) near the top of tain thrust sheet (Filer et al., 1996). Just to the northwest of
the Java Formation equivalents, about 1.4 m below the the sample locality, the strata are relatively flat lying, and
base of the equivalents of the lower Huron Shale (Fig. 3). the sampled interval is overlain by as much as 1650 m of
The Java Formation equivalents in the area consist of a the preserved younger Devonian, Mississippian, and lower
20 m thick interbedded sequence of thin (typically 0.3 to Pennsylvanian strata (Filer et al., 1996). The youngest,
1 m) organic-rich dark grey to black shales and thicker exposed lower Pennsylvanian strata contain bituminous
medium grey, organic poor shales. The sampled outcrop coals (Nolde et al., 1986; Henika, 1988), attesting to the
exposes the upper 18 m of the Java Formation (Fig. 3). significantly deeper burial by some point in the Late
Black shale-grey shale cyclicity is a basin wide phenom- Paleozoic. Based on the regional conodont alteration index
enon in the Java and older units, and the black shales have and the vitrinite reflectance data (Harris, 1978; Struble,

Fig. 2. Location of the section sampled. The solid line is a composite estimated shoreline with sediment input points labeled as lobes.
 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14 5

Fig. 3. Stratigraphic nomenclature applied to the study area in the Appalachian Basin. Shading indicates the two fourth-order basinwide sedimentation
cycles to be sampled.

1983), a maximum heating in the vicinity of 100–120 °C average upper crustal source (∼1.5 to 1.8 Ga) for
and the burial depth of about 3.5 km, assuming a typical Ordovician age (ca. 460 Ma) Welsh Basin sediments
geothermal gradient are likely (Hunt, 1979). (Thorogood, 1990; Evans, 1992; Lev et al., 1999).
According to Thorogood, the only deviations from this
3. Provenance and black shale processes in the source character are excursions toward younger values
Welsh Basin that are consistent with input from a volcanic arc source
during the Llanvirn and Caradoc. The source of the
Previously published Sm–Nd whole rock (shale) volcanic arc component is likely ash from active
isotopic data from the Welsh Basin suggest a uniform volcanism in the southern portion of the Welsh Basin

Fig. 4. Stratigraphic column of the section sampled. Total organic carbon (TOC wt.%) values are listed with the sample numbers.
6 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14

however, a number of older model ages are also reported

(i.e. N1.8 Ga). According to Lev et al. (1999) it is possible
that diagenetic REE redistribution and the Sm–Nd
isotopic resetting could produce a similar deviation in
the model ages and can account for both the young and the
old ages.

3.1. REE resetting

In Fig. 6 the expected range in provenance ages (1.5–

1.8 Ga) for the Welsh Basin, a volcanic arc source (1.0 Ga)
and a predicted path for diagenetic resetting (460 Ma) are
plotted. Mixing between a 1.6 Ga source and a 1.0 Ga
volcanic arc component will move an average shale
toward the 1.0 Ga field. This pattern is evident in several
samples from the Thorogood study. However, there is also
Fig. 5. A histogram showing the range of Nd model ages from mid- evidence for isotopic resetting which will move average
Ordovician age Welsh Basin shales (Thorogood, 1990; Evans, 1992; shale from the Welsh Basin along the REE redistribution
Lev et al., 1999). These rocks overlap the expected range in Nd model
ages for the Welsh Basin but, exhibit anomalously old and young ages. path. The samples with a likely volcanic arc component
These ages can be explained by mixing or diagenetic redistribution of have relatively young TDMs (i.e., 1.2 Ga) and an Sm/Nd
REE at or near the time of deposition. typical for the upper crustal shales exhibiting mixing
between a 1.6 Ga source and a 1.0 Ga volcanic arc
during the Llanvirn and to the north during the Caradoc. component. Whereas, diagenetically disturbed rocks
The model age of these sources is about 1.0 Ga therefore, which lie along the projected resetting pathway exhibit a
addition of this component would tend to yield a depleted range in model ages and 147Sm/144Nd ratios. A relatively
mantle model age (TDM) between 1.65 (average prove- old model age and a high 147Sm/144Nd is indicative of
nance age) and 1.0 Ga. Such a range is observed (Fig. 5), significant isotopic redistribution near the time of

Fig. 6. Plot of depleted mantle model age (TDM) vs. 147Sm/144Nd demonstrating the effects of changing 147Sm/143Nd on Nd model age. The dashed
line represents the pathway a normal Ordovician shale from the Welsh basin would follow by increasing and decreasing 147Sm/144Nd at the time of
sedimentation (e.g. 460 Ma). Data from work by Lev et al. (1999), Evans (1992), and Thorogood (1990) are plotted and exhibit an unusually large
range of 147Sm/144Nd values for shales derived from the upper crust. In addition these rocks lie outside the expected provenance range for the Welsh
Basin and lie along the predicted path for the diagenetic redistribution of REE.
 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14 7

identify the corrupted provenance information as well

as the post-depositional events in the history of a
sedimentary basin.

3.2. Uranium enrichment

Despite the evidence for a diagenetic REE resetting

event and the presence of relatively high organic matter
content (see Lev, 1994) in the Welsh basin shales, the
sequence investigated by the authors does not exhibit
evidence of syn-depositional U-enrichment. Instead, the
U–Pb isotopic whole systematics have apparently been
disturbed during a Permo-Triassic fluid event. U–Pb data
from Lev et al. (2000) are plotted on an isochron diagram
in Fig. 8. The isotopic character of the rocks studied have
Fig. 7. A Sm–Nd isochron diagram plotting Ordovician-age Welsh been altered at about 193 Ma, considerably after the time
Basin shales. Also plotted are fields representing a typical range in of deposition (ca. 460 Ma) hence, obscuring any
147
Sm/144Nd for the upper crust (Taylor and McLennan, 1985) and the provenance or paleo-environmental information pre-
volcanic arc component present in the Welsh Basin. Additionally, three
served during deposition. This timing coincides with a
reference lines are plotted for 1.65, 1.0 Ga and 460 Ma. Welsh Basin
data mainly lie along the 460 Ma reference line. Some points also lie significant period of hydrothermal activity in England,
along the 1.65 Ga reference line and along a sub-parallel path between Wales, and Ireland related to rifting associated with the
the 1.65 Ga line and the volcanic arc component indicating the opening of the Atlantic Ocean. In addition, the presence of
possibility of mixing between these sources. The rocks that lie along chalcopyrite, native gold and other metals (e.g. Ag, W, U,
the 460 Ma line are clearly reset during the Ordovician likely at the
Th and Pb) clearly present as late diagenetic trace phases
time of sedimentation.
in these shales (Lev et al., 2000) supports the notion that
the U–Pb whole rock isotopic system has been reset by
sedimentation associated with the addition of REE-rich these fluids. This resetting event was possible due to the
phases with high Sm/Nd ratios (e.g. diagenetic apatite) or organic-rich nature of the shales, a feature obviously
loss of LREE enriched low Sm/Nd phases (e.g., monazite) unique to black shales.
at about the time of sedimentation. The exact opposite
occurring at about the time of sedimentation is true for a
sample with a relatively young model age. The potential
timing of the resetting event is evident when Welsh Basin
data is plotted on a Sm–Nd isochron diagram (Fig. 7). The
data presented here suggest a REE redistribution event at
about the time of deposition for these middle Ordovician
shales.
The examination of regional whole rock data from
Wales suggests that isotopic resetting may be a more
common process than was generally appreciated in
the past. Although the nature of the resetting cannot
specifically be determined from the data available, it
is reasonable to propose diagenetic resetting as
the cause due to the timing and similarity to the effected
Llandeilo–Caradoc black shales. If this is the case, it
should be possible to identify diagenetically affected
shales from a related stratigraphic sequence based on
their Sm–Nd isotopic systematics. The ultimate cause Fig. 8. 206Pb/204Pb vs. 238U/204Pb isochron diagram with Llandeilo–
of any given disturbance must be evaluated using a Caradoc formation whole rock samples from Lev et al. (2000). Whole
rocks deposited at about 460 Ma lie along a 193 Ma reference line.
petrographic approach similar to that of Lev et al. This age is clearly younger than the time of deposition (ca. 460 Ma)
(1998). In the case of the Sm–Nd isotopic system, an and represents a late diagenetic redistribution of U with in the
integrated geochemical and petrographic approach will Llandeilo–Caradoc Formation.
8 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14

4. Provenance and black shale processes in the

southern Appalachian Basin

Sediments deposited in the Appalachian Basin are

representative of the source areas exposed throughout the
long depositional history of the basin (Ordovician–
Devonian?). The rocks examined here were deposited in
the Appalachian foreland basin during a part of the
Devonian Acadian orogeny. Currently, the nature of the
Acadian hinterland is poorly known. By the time of that
event, terranes had been accreted to the Laurentian
continental margin, of Grenville age, during the Ordovi-
cian orogenesis related to the closing of Iapetus. Possible
sources of Acadian sediment, then, include the Mesopro-
terozoic Laurentian margin and the recycled sediments
deposited on that margin during the opening of Iapetus. Fig. 9. A Sm–Nd isochron diagram plotting Devonian-age Appala-
These sediments potentially carry a signature from a large chian Basin shales. Also plotted are two reference lines for 1.3 Ga and
part of the craton, and were affected by the Early Paleozoic 365 Ma. Appalachian Basin data mainly lie along the 365 Ma reference
orogenisis. Additional potential sources include terranes line reflecting a resetting event during the Devonian at about time of
sedimentation.
accreted during the Early Paleozoic orogenesis, sediment
deposited in the Early Paleozoic foreland basin created by
terrane accretion (possibly carrying their own diverse than 1.64 Ga exhibit a high 147Sm/143Nd (N 0.12) for rocks
signature), and the landmass or landmasses that collided derived from the upper crust. This, along with the presence
with Laurentia and caused the Acadian orogeny itself. of organic matter, requires that the Sm–Nd isotopic data
These possibilities suggest the major source of sediment be more carefully evaluated. If the ɛNd is recalculated at
during the Devonian was Grenville-aged rocks, older the time of deposition (Table 1), the range in the isotopic
Laurentian (ca. 1.8 Ga) components, and recycled sedi- composition is minimized to (ɛNd(365) −7.68 to −8.01))
ments also carrying a predominantly Grevillian prove- and appears to be dominated by a Grenvillian source. This
nance signature. suggests that the Sm–Nd isotopic system has been reset
during diagenesis.
4.1. REE redistribution The Sm–Nd isochron diagram in Fig. 9 confirms that
the REE were likely redistributed at about the time of
Nd isotopic data from organic-rich shales in the study deposition. Plotted on the diagram are reference lines with
are presented here for the first time (Table 1). The range of slopes of 1.3 Ga and 365 Ma. The Devonian black shales
Nd model ages for these rocks (1.64 to 2.04 Ga) suggest from this study with a 147Sm/143Nd N 0.12 clearly lie along
that the primary source is oldest Grenville possibly with the 365 Ma line requiring at least partial resetting of the
some contribution from an Archean source (e.g. Superior Sm–Nd isotopic system at about the time of deposition. If
Province). However, all of the samples with TDMs older the same samples are examined in 147Sm/143Nd vs. time

Table 1
Whole rock Sm–Nd isotope data from Java Formation shales with in the Appalachian Basin
Sample ID Sm (ppm) Nd (ppm) 147
Sm/144Nd 143
Nd/144Nd ɛNd Today ɛNd 365 Ma TDM (Ga)

BSG 16 37.49 7.75 0.1257 0.512073 −10.98 − 7.68 1.79

BSG 17 40.88 8.93 0.1329 0.512077 −10.90 − 7.94 1.94
BSG 19 42.36 9.63 0.1384 0.512096 −10.53 − 7.82 2.04
BSG 20 32.05 5.94 0.1127 0.512025 − 11.92 − 8.01 1.64
BSG 21 40.24 9.06 0.1371 0.512088 −10.69 − 7.92 2.02
BSG 24 42.57 8.96 0.1281 0.512071 − 11.02 − 7.83 1.84
Values normalized to a 146Nd/144Nd = 0.7219 and corrected to correspond to a 143Nd/144Nd value of 0.511856 for the La Jolla Nd standard (measured
La Jolla = 0.511844).
ɛNd(t) is calculated as: [(143Nd/144Ndsample / 143Nd/144NdCHUR − 1)⁎104].
TDM is calculated as: 1 / l ⁎ ln[((143Nd/144Nd)sample −0.51315) / (147Sm/144Nd)sample / 0.217) = 1].
Uncertainty on the 143Nd/144Nd measurements is better than +/−0.2 ɛ units.
 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14 9

Fig. 10. Plot of depleted mantle model age (TDM) vs. 147Sm/144Nd demonstrating the effects of changing 147Sm/143Nd on Nd model age. The dashed
line represents the pathway a normal Devonian shale from the southern Appalachian basin would follow by increasing and decreasing 147Sm/144Nd at
the time of sedimentation (e.g. 365 Ma). These rocks lie outside the expected provenance range for the southern Appalachian Basin and lie along the
predicted path for the diagenetic redistribution of REE.

space, this redistribution event is clear (Fig. 10). As in the sition for this sequence. If the effects of the U-enrichment
case of the Welsh Basin shales, these Appalachian Basin on the Pb isotope system are accounted for, the whole rock
shales seem to have been affected by a syn-/post-depo- Pb isotopic signature at the time of deposition can be
sitional process capable of redistributing the REE. REE recovered. This type of correction has been applied by Lev
whole rock data and associated modeling for these rocks
published elsewhere (Lev and Filer, 2004) suggest that the
formation of a REE-bearing phase (i.e. apatite) during the
early diagenetic black shale processes discussed previ-
ously, is likely responsible for the disturbance of the Sm–
Nd system.

4.2. Uranium enrichment

The Appalachian Basin shales from this Devonian

sequence are enriched in U relative to the upper crust and
average shale and there is a favorable correlation between
organic content and U concentration (Fig. 11). This
correlation reflects the dissolved oxygen conditions
present at or near the sediment:water interface during
deposition and early diagenesis given the reducing
conditions required for the preservation of organic matter.
If this model is correct, the uranium sequested in the
sediments will undergo radioactive decay. Pb will
accumulate in the shale potentially altering the Pb isotopic Fig. 11. Plot of whole-rock U/Pb ratios vs. U concentrations (ppm)
composition of the whole rock. Fig. 12 is an isochron from Lev and Filer (in press). Samples generally reflect elevated U
concentrations relative to North American Shale Composite (Condie,
diagram for the 238U–206Pb isotope system. The Appa- 1993) and are positively correlated with Total Organic Content (Wt.%)
lachian shales form an array with a slope of about 365 Ma (see inset) indicating that U enrichment likely occurred at or near the
(340± 50 Ma), which is the approximate time of depo- time of deposition.
10 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14

5. Black shale REE systematics

There is mounting evidence that the REE are mobile

during black shale diagenesis (Elderfield et al., 1985;
Elderfield and Sholkovitz, 1987; Milodowski and Zala-
siewicz, 1991; Murray et al., 1991; Ohr et al., 1991, 1994;
Bock et al., 1994; Bouch et al., 1995; Cullers et al., 1997;
Lev et al., 1998, 1999; McLennan et al., 2003; Kidder
et al., 2003). To date the most diagnostic evidence for the
REE redistribution in a source related sequence of black
shales is the whole rock 147Sm/144Nd. The 147Sm/144Nd is
indicative of the shape of the LREE (La–Sm) portion of
the whole rock REE pattern. In a typical shale the REE are
derived primarily from detrital components and are
Fig. 12. 206Pb/204Pb vs. 238U/204Pb isochron diagram from Lev and therefore similar to the REE content of the upper crust
Filer (in press) with Devonian age Appalachian Basin whole rock
in the source area (Taylor and McLennan, 1985). The
samples plotted. Shales lie along a 340 ± 50 Ma isochron which 147
corresponds to the approximate age of deposition. This age suggests a Sm/144Nd for upper crustal shales is generally between
redistribution of U sometime after the time of deposition. 0.10 and 0.12. Shales that have experienced post-
depositional REE redistribution on a scale greater than a
and Filer (2004) and the results are plotted in Fig. 13. At hand sample will typically lie outside of this range and
the time of deposition, the Devonian Appalachian shales contain some evidence (petrographic or geochemical) for
have an isotopic composition similar to the Grenville the formation and later the dissolution and loss, in some
dominated Ordovician-aged shales from the northern cases, of the LREE-enriched phosphates (Milodowski and
Appalachian Basin (Fig. 13, Lev and Filer, 2004). This Zalasiewicz, 1991; Ohr et al., 1991, 1994; Bock et al.,
corrected Pb isotopic data supports the results of the Nd 1994; Cullers et al., 1997; Lev et al., 1998, 1999;
isotopic data corrected for diagenetic effects from the McLennan et al., 2003; Kidder et al., 2003).
same rocks. The syn-/post-depositional conditions re- The effect that the open-system precipitation/dissolu-
sponsible for the enrichment of uranium in these shales are tion of a REE-enriched diagenetic phosphate can have on
a common black shale process. the REE content and the 147Sm/144Nd of an average shale

Fig. 13. Devonian age Appalachian Basin shales from Lev and Filer (in press) (black squares) are plotted in 206Pb/204Pb vs. 207Pb/204Pb space. Also
plotted are a Stacey and Kramers (1975) and μ = 8 Pb evolution curve along with a reference line showing Pb evolution from 365 to today. The white
squares are the Pb isotopic compositions re-calculated at the time of deposition (365 Ma). The re-calculated Pb isotopic compositions overlap a field of
Ordovician age shales from the northern Appalachian Basin with a predominantly Grenville aged source, possibly indicating a similar source character.
 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14 11

accompanying alteration is presented in Fig. 15. Although

the potential for the dissolution/precipitation of REE
bearing phases exists in many detrital systems, it is most
commonly found in black shale systems (Lev et al., 1998,
1999 and references therein). A likely reason for this
pattern is the aggressive pore water chemistry and
conditions conducive to REE-bearing phosphate forma-
tion that can develop during the diagenetic breakdown of
the organic matter (Lev et al., 1998 and references therein).

6. Uranium enrichment in black shales

Metal enrichment in the black shale systems typically

occurs either during deposition under the reducing
conditions at or near the sediment–water interface or
Fig. 14. A chondrite normalized plot demonstrating the effects of the during a post-/syn-depositional fluid mineralizing fluid
REE redistribution on the North American Shale Composite (NASC)
event. Under either set of circumstances the metal content
(Condie, 1993). The upper pattern reflects the growth of a REE-
enriched phase during diagenesis while the depleted pattern is of the detrital component in the shales will be significantly
indicative of redistribution and then later loss of the meta-stable altered. While this enrichment provides a record of the
REE-enriched phase. redox conditions within the basin at or near the time of
deposition, it may serve to obscure the trace metal sig-
has been documented elsewhere and is demonstrated in nature of the source area. In the case of uranium, this
Fig. 14 (Milodowski and Zalasiewicz, 1991; Ohr et al., disturbance will also impact the Pb isotopic composition
1991, 1994; Bock et al., 1994; Cullers et al., 1997; Lev of the shale, which would reflect the Pb isotopic character
et al., 1998, 1999; McLennan et al., 2003; Kidder et al., of the source area. Instead, the U–Pb isotope system will
2003; Lev and Filer, 2004) This change in the REE pattern record the timing and extent of uranium enrichment for a
will also impact the evolution of the Sm–Nd isotopic given shale. This type of uranium enrichment during
system and in turn the Nd model age of the shale. This diagenesis and the associated isotopic resetting has been

Fig. 15. Plot of TDM vs. 147Sm/144Nd demonstrating the effects of a changing 147Sm/143Nd on Nd model age. The dashed line represents the pathway a
normal shale with a model are in the range of 1.5 to 1.8 Ga would follow by increasing and decreasing 147Sm/144Nd at the time of sedimentation (e.g.
460 Ma).
12 S.M. Lev et al. / Earth-Science Reviews 86 (2008) 1–14

yield useful provenance information if the post-deposi-

tional history can be well characterized. For example, the
alteration of the Devonian shales from the southern
Appalachian Basin clearly occurred at about the time of
deposition based on the resetting of the Sm–Nd and U–Pb
isotopic system at that time. As a result, it is valid to
evaluate the provenance signature at the time of the
resetting event. Specifically, the isotopic evolution that has
occurred since the resetting event should be subtracted
leaving the initial isotopic character of the whole rock at
the time of deposition. This approach is only appropriate
for a system with a two-stage history similar to the Sm–Nd
and U–Pb systems in the Appalachian Basin sediments
and the Sm–Nd system in the Welsh Basin sediments
investigated.

Acknowledgements
Fig. 16. Plot of U/Pb ratios vs. U concentrations (ppm) with a pathway
illustrating the effect on NASC during syn-depositional gain of U. Acknowledgement is made to the donors of The
Petroleum Research Fund, administered by the American
documented previously and a model of this process is Chemical Society, for support of this research. Support
presented in Fig. 16 (Lev et al., 2000; Lev and Filer, 2004). was also provided by National Science Foundation grant
DMR 0116619.
7. Black shale alteration and provenance
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