Geochemistry 3 Characterization

G
Volume 2

Geophysics April 20, 2001

Geosystems Paper number 2000GC000109

ISSN: 1525-2027
AN ELECTRONIC JOURNAL OF THE EARTH SCIENCES
Published by AGU and the Geochemical Society

Relationships between the trace element

composition of sedimentary rocks and upper
continental crust
Scott M. McLennan
Department of Geosciences, State University of New York at Stony Brook, Stony Brook, New York 11794-2100
(Scott.McLennan@sunysb.edu)

[1] Abstract: Estimates of the average composition of various Precambrian shields and a variety of
estimates of the average composition of upper continental crust show considerable disagreement for a
number of trace elements, including Ti, Nb, Ta, Cs, Cr, Ni, V, and Co. For these elements and others that
are carried predominantly in terrigenous sediment, rather than in solution (and ultimately into chemical
sediment), during the erosion of continents the La/element ratio is relatively uniform in clastic sediments.
Since the average rare earth element (REE) pattern of terrigenous sediment is widely accepted to reflect the
upper continental crust, such correlations provide robust estimates of upper crustal abundances for these
trace elements directly from the sedimentary data. Suggested revisions to the upper crustal abundances of
Taylor and McLennan [1985] are as follows (all in parts per million): Sc = 13.6, Ti = 4100, V = 107, Cr =
83, Co = 17, Ni = 44, Nb = 12, Cs = 4.6, Ta = 1.0, and Pb = 17. The upper crustal abundances of Rb, Zr, Ba,
Hf, and Th were also directly reevaluated and K, U, and Rb indirectly evaluated (by assuming Th/U, K/U,
and K/Rb ratios), and no revisions are warranted for these elements. In the models of crustal composition
proposed by Taylor and McLennan [1985] the lower continental crust (75% of the entire crust) is
determined by subtraction of the upper crust (25%) from a model composition for the bulk crust, and
accordingly, these changes also necessitate revisions to lower crustal abundances for these elements.

Keywords: Geochemistry; composition of the crust; trace elements.

Index terms: Crustal evolution; composition of the crust; trace elements.
Received September 8, 2000; Revised December 3, 2000; Accepted December 11, 2000;
Published April 20, 2001.

McLennan, S. M., 2001. Relationships between the trace element composition of sedimentary rocks and upper
continental crust, Geochem. Geophys. Geosyst., vol. 2, Paper number 2000GC000109 [8994 words, 10 figures, 5
tables]. Published April 20, 2001.

Theme: Geochemical Earth Reference Model (GERM) Guest Editor: Hubert Staudigel

1. Introduction
understanding the composition and chemical
[2]The chemical composition of the upper differentiation of the continental crust as a
continental crust is an important constraint on whole and the Earth in general [e.g., Taylor

Copyright 2001 by the American Geophysical Union

 Geochemistry 3 mclennan: trace element composition and upper continental crust
Geophysics
Geosystems G
and McLennan, 1985, 1995; Rudnick and
Fountain, 1995]. There have been a variety of
estimates of upper crustal composition mostly
based on large-scale sampling programs, largely
in Precambrian shield areas, geochemical com-
pilations of upper crustal lithologies, and sedi-
mentary rock compositions (mainly shales). If
the average chemical composition of the upper
crust can be estimated from sedimentary rocks,
then an especially powerful insight may be
gained into the chemical evolution of the crust
(and Earth) over geological time because of the
relatively continuous record of sedimentary
rocks, dating from 4 Ga to the present.
[3] For the most part, estimates of upper crustal
abundances from sedimentary data have been
restricted intentionally to trace elements that are
least fractionated by various sedimentary pro-
cesses, such as chemical and physical weath-
ering, mineral sorting during transport, and
diagenesis [McLennan et al., 1980]. Included
are the rare earth elements (REE), Th, and Sc as
well as other elements (K, U, and Rb) that can
be estimated indirectly using various so-called
canonical ratios (Th/U, K/U, and K/Rb).
Recently, however, this general approach has
been applied to other trace elements, notably
Nb, Ta, and Cs that at least potentially, may be
more affected by various sedimentary processes
[e.g., McDonough et al., 1992; Plank and
Langmuir, 1998; Barth et al., 2000]. In this
paper the relationships between the trace ele-
ment composition of the sedimentary mass and
the upper continental crust are evaluated for a
variety of trace elements and new estimates of
upper crustal trace element abundances, based
on the sedimentary rock record, are presented.
2. Comparison of Upper Crustal
Estimates
[4] The most commonly cited estimates of
upper crustal abundances are those of Taylor
and McLennan [1985] (hereinafter referred to
2000GC000109
as TM85), which are based on a variety of
approaches for different elements, including
large-scale sampling programs (e.g., major ele-
ments, Sr, and Nb), average igneous composi-
tions (e.g., Pb), compilations from Wedepohl
[1969±1978] (e.g., Ba and Zr), sedimentary
compositions (e.g., REE, Th, and Sc), and
various canonical or assumed ratios, such as
Zr/Hf, Th/U, K/U, K/Rb, Rb/Cs, and Nb/Ta
(e.g., Hf, U, Rb, Cs, and Ta). Although there is
widespread agreement that the upper crust
approximates to a composition equivalent to
the igneous rock type granodiorite, there is in
fact considerable disagreement regarding the
precise values of a variety of trace elements.
In Table 1, estimates of selected trace elements
are tabulated for various shield surfaces. Some
of these compositions are compared to the
upper crustal estimate of TM85 in Figure 1,
where it can be seen that discrepancies by
nearly a factor 2 or more are common and that
in some cases, estimates differ by more than a
factor of 3 (Nb, Cr, and Co). These differences
are likely due to some combination of inad-
equate sampling, analytical difficulties, and real
regional variations in upper crustal abundances.
In Table 2, various other recent estimates of the
upper crust (see Table 2 for methods of esti-
mates) are also compared to TM85, and again,
some significant differences can be seen.
3. Sedimentary Rocks and Upper
Crustal Compositions
[5] The notion that sediments could be used to
estimate average igneous compositions at the
Earth's surface was first suggested by V. M.
Goldschmidt (see discussion by Goldschmidt
[1954, pp. 53±56]), and using sedimentary data
to derive upper crustal REE abundances was
pioneered by S. R. Taylor [e.g., Taylor, 1964,
1977; Jakes and Taylor, 1974; Nance and
Taylor, 1976, 1977; McLennan et al., 1980;
Taylor and McLennan, 1981, 1985]. Gold-
schmidt used glacial sediments to estimate the
Table 1. Selected Trace Elements for Estimates of Various Shield Areas and the Average Upper Continental Crust

Geosystems
Geophysics
Geochemistry
Element, Canadian Canadian East Scotlandd New Coloradof Baltic Ukranian Anabar Average Average Upper
ppm Shield: Shield: Eade Chinac Mexicoe Shieldg Shieldh Shieldi Shieldj Shield Crustl
Shawa and Fahrigb (Area)k
Sc 7.0 12 15 16 12 10.3 11

G
Ti 3120 3180 3900 2400 2700 4200 3000 3000 4800 3400 3200 3000
V 53 59 98 70 62 60

3 mclennan: trace element composition and upper continental crust

Cr 35 76 80 <50 19 82 60 43 72 58 59 35
Co 12 17 35 8 17 18 13 10
Ni 19 19 38 25 13 43 25 27 33 27 23 20
Rb 110 82 85 187 72 77 125 63 100 99 112
Zr 237 190 188 135 180 148 117 154 197 172 186 190
Nb 26 12 4 9.1 11 10 12 (23) 25
Cs 3.55 3.6 3.6 3.7
Ba 1070 730 678 795 590 749 420 701 775 723 754 550
La 32.3 71 34.8 55 43 27 23 45 32 40 (43) 30
Hf 5.8 5.12 4.4 5.1 5.7 5.8
Ta 5.7 0.74 0.67





2.2
Pb 17 18 18 14 17 18 20
Th 10.3 10.8 8.95 13 6.2 7.9 14 10.2 9.8 10.7

Area, 106km2 5.56 0.95 0.01 0.05 0.02 2.16 0.20 0.06
a
Average Canadian Shield values from Shaw et al. [1967, 1976, 1986].
b
Average Canadian Shield values from Fahrig and Eade [1968] and Eade and Fahrig [1971, 1973].
c
Average central East China calculated on carbonate-free basis [Gao et al., 1998].
d
Average of crystalline basement NW Scotland Highlands [Bowes, 1972].
e
Average Precambrian surface terrane, New Mexico [Condie and Brookins, 1980].
f
Average of Colorado Plateau upper crust derived from equal proportions of northwest and southeast sections [Condie and Selverstone, 1999].
g
Average Baltic Shield (reported by Borodin [1999]).
h
Average Ukranian Shield (reported by Borodin [1999]).
i
Average Anabar Shield (reported by Borodin [1999]).
j
Average shield derived from simple average of the Canadian Shield to the Anbar Shield columns.
k
Average shield derived from weighted average by area of the Canadian Shield (average of both Shaw and Eade and Fahrig) to the Anbar Shield. Areas are taken from Goodwin

2000GC000109
[1991]. Note that La = 31 ppm if Canadian Shield values from Eade and Fahrig are excluded, Nb = 11 ppm if Canadian Shield from Shaw and Scotland are excluded, and Ta is not
calculated owing to highly variable values.
l
Average upper continental crust [Taylor and McLennan, 1985].
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
1000 tuting up to 70% of the stratigraphic record
Canadian Shield Ba
(Shaw) (depending on the method of estimating), and
Canadian Shield
(Eade & Fahrig)
because most trace elements are enriched in
shales compared to most other sediment types.
Shield Estimate

Zr
The result is that shales dominate the sedimen-
100
tary mass balance for all but a few trace
Rb
elements.
La V
Cr
[6] Most studies also have been restricted to a
Ni Nb few trace elements that are least affected by
Th
Pb sedimentary processes and are transferred dom-
10
Co (a) inantly into the clastic sedimentary record dur-
ing continental erosion, notably REE, Y, Sc,
1000
10 100 1000 and Th. However, there are numerous other
China Ba trace elements that are transferred from upper
Scotland crust primarily into the clastic sedimentary
New Mexico mass, including Zr, Hf, Nb, Ta, Rb, Cs, Pb,
Shield Estimate

Colorado
100
V
La
Co
Pb
Cr
10 Ni
Th Nb
10
Taylor & McLennan Upper Crust
Figure 1. Comparison plots for selected trace
elements in two independent estimates of the
Canadian Shield surface and various other shields
with the estimate of the average upper continental
crust from Taylor and McLennan [1985]. Thick
solid line represents equal compositions, and dashed
lines represent difference by a factor of 2. Data are
from Table 1.
major element composition of average igneous
rocks because such sediment is dominated by
mechanical rather than chemical processes.
However, modern studies have used shale
compositions to estimate upper crustal trace
element abundances (TM85). This is because
shales completely dominate the sedimentary
record [Garrels and Mackenzie, 1971], consti-
Cr, V, Ni, and Co. Until recently, these ele-
Zr
ments have been largely neglected (see discus-
sion by TM85) because of perceived problems
Rb
of fractionation during mineral sorting, such
that shales may not dominate the sedimentary
mass balance (e.g., Zr, Hf, Nb, Ta, and Pb), and
possible redistribution during weathering and/
or diagenesis (e.g., Rb, Cs, Pb, Cr, V, Ni, and
(b) Co). Given the large variability among the
100 1000
various upper crustal and shield estimates for
these elements (Tables 1 and 2), such processes
may well add relatively minor uncertainty to
upper crustal estimates derived from the clastic
sedimentary record.
3.1. Cs in the Upper Crust
[7] The Cs content of the upper crust is given as
3.7 ppm by TM85 based on a Rb content of
112 ppm and a Rb/Cs ratio of 30. McDonough
et al. [1992] argued that there was no fractio-
nation of Rb from Cs during sedimentary
processes and determined the average Rb/Cs
of 140 sediments and sedimentary rocks to be
19 (standard deviation of 11), which he took to
be equivalent to the upper crust and leading to
an upper crustal Cs content of 6 ppm (using
the Shaw et al. [1986] Canadian Shield average
of Rb = 110 ppm). Rudnick and Fountain
 Geosystems
Geophysics
Geochemistry
Table 2. Selected Estimates of the Average Composition of the Upper Continental Crust

G
Element Condie Condie Gaillardet et al.c Togashi et Wedepohle Plank & Langmuirf Boroding Taylor and Upper
(ppm) ``Map''a ``Restoration''b al.d McLennanh Crusti

3 mclennan: trace element composition and upper continental crust

Sc 13.3 13.4 10.5 16 11 13.6
Ti 3300 3200 3700 4555 3600 3000 4100
V 86 86 110 60 107
Cr 104 112 74 84 47 35 83
Co 18 18 13 15 10 17
Ni 56 60 50 38 21 20 44
Rb 83 87 108 85 108 112 (112)
Zr 160 162 89 135 175 190 (190)
Nb 9.8 10.3 9 13.7 12 25 12
Cs 2.7 5.5 5.8 7.3 3.7 4.6
Ba 633 626 630 458 668 705 550 (550)
La 28.4 29.0 29.7 21.7 33 30 (30)
Hf 4.3 4.4 2.1 4.1 5.8 (5.8)
Ta 0.79 0.82 0.9 0.72 1.5 0.96 2.2 1.0
Pb 17 18 17.9 16.9 20 17
Th 8.6 9.1 8.8 8.3 11 10.7 (10.7)
a
Average upper continental crust from ``map model'' of major upper crustal lithologies [Condie, 1993].
b
Average upper continental crust from ``resoration model,'' where eroded crust is accounted for [Condie, 1993].
c
Average upper crust in Central African Shield derived from ``corrected'' river suspended sediment in Congo River system [Gaillardet et al., 1995].
d
Average upper crust for the Japan Arc based on mapped lithological balances [Togashi et al., 2000].
e
Average upper crust for elements not taken from Shaw et al. [1986] [Wedepohl, 1995]. Cs derived from Rb/Cs = 19 [McDonough et al., 1992] and Shaw et al. [1986] Rb value; Ta
derived from Nb/Ta = 17.5 and Shaw et al. [1986] Nb value.
f
Upper continental crust derived from marine sedimentary record [Plank and Langmuir, 1998].
g
Upper continental crust estimated by weighting average shields (70%) and average granitoid rock (30%) [Borodin, 1999].
h
Average upper crust [Taylor and McLennan, 1985].

2000GC000109
i
Average upper continental crust derived from sedimentary record for this study. Elements that are unchanged from Taylor and McLennan [1985] are shown in parentheses.
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
[1995] adopted an upper crustal Rb/Cs ratio of 30
(a)
20 and reported a Cs content of 5.6 ppm (using
the TM85 upper crustal value of Rb = 112
ppm). Recently, the TM85 estimate has also

Rb/Cs
Unweathered
been questioned by Plank and Langmuir 25
Granodiorite
[1998] on the basis of young marine sedimen-
tary data. They noted a correlation between Cs
and Rb in modern deep-sea sediments from a
variety of tectonic and sedimentological 20

regimes. Using this correlation and accepting Granodiorite

a Rb upper crustal abundance of 112 ppm, they Weathering Profile
derived a new Cs estimate of 7.3 ppm (imply- (Nesbitt & Markovics 1997)

ing an upper crustal Rb/Cs of 15.3). 15

70 90 110 130 150
30
[8] The behavior of Cs in the sedimentary (b)
environment, in fact, is not well documented. 25
Unweathered
Basalt
On the basis of the data available at the time, Rb/Cs
McDonough et al. [1992] argued that the Rb/Cs 20
ratio does not change during sedimentary pro-
cesses. However, this conclusion does not seem 15
to be consistent with the observations that sea-
water Rb/Cs is 400, typical river water Rb/Cs 10
is 50 [e.g., TM85; Lisitzin, 1996], and some
Basalt
tropical river waters have ratios in excess of 5 Weathering Profile
1000 [Dupre et al., 1996], whereas all workers (Price et al., 1991; S. R. Taylor, 1997)

seem to agree that the upper crustal Rb/Cs is 0

<40 [TM85; McDonough et al., 1992; Gao et
al., 1998; Wedepohl, 1995; Rudnick and Foun-
tain, 1995; Plank and Langmuir, 1998].
[9] Rb/Cs ratios of weathering profiles appear
to change systematically as a function of Rb
content in both basaltic and granitic terranes
(Figure 2), suggesting at least the potential for
fractionation between these elements during
surficial processes. Dupre et al. [1996] found
Congo River suspended sediment, bed load
sands, and dissolved load (including colloids)
to have the following Rb/Cs ratios (average
‹95% confidence interval): 17 ‹ 4 (n = 8), 47 ‹
8 (n = 15), and 481 ‹ 454 (n = 8), respectively,
and Gaillardet et al. [1997] found Rb/Cs ratios
as low as 4 in suspended sediment from the
Amazon River. Thus interaction of natural
waters with typical upper crust appears to
0 10 20 30 40
Rb (ppm)
Figure 2. Plots of Rb/Cs versus Rb for weathering
profiles developed on granodiorite [Nesbitt and
Markovics, 1997] and basalt ([Price et al., 1991] Cs
data from S. R. Taylor (personal communication,
1997)) in Australia, suggesting Rb/Cs ratios may be
strongly fractionated within weathering profiles. In
spite of any fractionation within soil profiles both of
these elements are carried from weathering sites
predominantly in the particulate load.
lower the Rb/Cs ratio in the resulting fine-
grained clastic sediments, likely due to the
preferential exchange of the larger Cs ion onto
clay minerals.
[10] There are few reliable data for Cs in
carbonates, evaporites, and siliceous sediments;
 Geochemistry 3 mclennan: trace element composition and upper continental crust
Geophysics
Geosystems G
however, from simple crystal chemical argu-
ments the larger Cs ion would be expected to
be preferentially excluded compared to Rb in
most carbonate and evaporite minerals, leading
to relatively high Rb/Cs ratios compared to the
upper crust (see discussion regarding carbo-
nates by Okumura and Kitano [1986]). Thus,
although Rb and Cs are carried dominantly in
clastic sediments, it is not obvious that the Rb/
Cs ratio of marine sediment studied by Plank
and Langmuir [1998], where the terrigenous
fraction is dominated by very fine grained
clays, is fully representative of the upper crust.
3.2. Nb-Ta-Ti in the Upper Crust
[11] The Ti and Nb contents of the upper
continental crust are given as 3000 and 25
ppm, respectively, by TM85 on the basis of
the large-scale sampling program in the Cana-
dian Shield by D. M. Shaw [Shaw et al., 1967,
1976, 1986], and the Ta estimate of 2.2 ppm is
based on a crustal Nb/Ta ratio of 11.6 (taken
from Wedepohl [1977]). Recently, these esti-
mates also have been questioned by Plank and
Langmuir [1998] on the basis of sedimentary
data. Plank and Langmuir [1998] noted corre-
lations between Nb and Al2O3, between Ti and
Al2O3, and between Nb and Ta in modern
deep-sea sediments from a variety of tectonic
and sedimentological regimes. From these rela-
tionships and by accepting the Al2O3 upper
crustal estimate of TM85 they estimated TiO2
at 0.76%, Nb at 13.7 ppm, and Ta at 0.96 ppm.
Barth et al. [2000] suggested estimates of Nb =
11.5 ppm and Ta = 0.92 ppm on the basis of the
abundances of these elements in Australian
post-Archean shales (PAAS) and loess.
[12] It has long been known that elements
concentrated in heavy mineral suites (notably,
Zr and Hf but also Sn, Th, LREE, etc.) may be
strongly fractionated during mineral sorting of
clastic sediments [McLennan et al., 1993].
Although the geochemistry of Ti, Nb, and Ta
is likely to be less affected by such processes,
2000GC000109
these elements may be concentrated in heavy
mineral suites (e.g., rutile, ilmenite, anatase,
etc.), and like zircon, rutile and anatase are
``ultrastable'' heavy minerals [Pettijohn et al.,
1972]. Accordingly, some care must be taken in
interpreting the Ti, Nb, and Ta content of
shales. On the other hand, the discrepancy
between estimates of Plank and Langmuir
[1998; Barth et al., 2000] and for the Canadian
Shield [Shaw et al., 1986] is nearly a factor of
2, much greater than might be expected from
any of these sedimentological considerations.
3.3. Cr-Ni-V-Co in the Upper Crust
[13] Upper crustal ferromagnesian trace element
abundances reported by TM85, based largely
on the Canadian Shield estimates of Shaw et al.
[1967, 1976] and Eade and Fahrig [1971,
1973; Fahrig and Eade, 1968], are relatively
low (e.g., Cr = 35 ppm and Ni = 20 ppm)
compared to a number of other shield estimates
(Table 1 and Figure 1) and various other upper
crustal estimates (Table 2). In contrast, the
abundances of ferromagnesian trace elements
in shales are typically a factor of 2 greater
than these values (TM85). This discrepancy has
rarely been discussed in any detail, although
Condie [1993] has proposed significantly
higher upper crustal abundances of ferromag-
nesian trace element abundances (see Table 2).
[14] Relatively low upper crustal abundances of
these elements were effectively a requirement of
the once popular ``andesite model'' for crustal
growth because average andesite has very low
abundances for these elements [e.g., Taylor,
1967, 1977; Gill, 1981; Gill et al., 1994]. For
example, Taylor [1977] estimated average ande-
site to have Cr = 55 ppm and Ni = 30 ppm.
During intracrustal partial melting and differ-
entiation, enrichments of such elements in the
residual lower crust would be expected, but for
the andesite model, high ferromagnesian trace
element abundances in the upper crust (e.g., Cr
> 55 ppm) would have predicted the opposite
 Geochemistry 3 mclennan: trace element composition and upper continental crust
Geophysics
Geosystems G
and thus created mass balance difficulties.
Accordingly, the low levels of ferromagnesian
trace elements found in the Canadian Shield by
Shaw et al. [1967, 1976] seemed consistent.
[15] However, it is now understood that low
abundances of these elements in typical oro-
genic andesites are a reflection of the fractio-
nated nature of most andesites and that
unfractionated mantle-derived arc magmas
typically have much higher levels of ferro-
magnesian trace elements [e.g., Gill, 1981]. In
addition, it is now widely accepted that much
of the continental crust formed during the
Archean and higher ferromagnesian trace ele-
ment levels are characteristic of Archean oro-
genic igneous rocks [e.g., Condie, 1993].
Most models of bulk crustal abundances now
reflect these higher levels [Taylor and McLen-
nan, 1985, 1995; Rudnick and Fountain,
1995], but upper crustal abundances of the
ferromagnesian trace elements have received
little comment.
4. Methods
4.1. Database
[16] The database consists of a variety of com-
pilations based on large-scale averages or com-
posites of several sedimentary rock types of
different grain sizes and from a variety of
tectonic and sedimentological settings. Where
possible, old sedimentary rocks, especially of
Archean through early Proterozoic age, were
neglected in order to avoid any issues of secular
change in upper crustal composition. In fact,
even with this sampling strategy, it is impos-
sible to entirely avoid issues of secular varia-
tions in composition because most sedimentary
rocks are recycled over long periods of geo-
logical time [Veizer and Jansen, 1979, 1985].
[17] The Russian Shale average is based on a
remarkable number of samples (n  40,000).
2000GC000109
Apart from this, >1200 samples have gone into
the various other averages and composites.
Table 3 lists the trace element analyses and
data sources used in Figures 3±10. There is a
small amount of redundancy in some of these
averages in that the same samples may be
included in more than one of the averages.
For example, modern turbidites analyzed by
McLennan et al. [1990] are subdivided by
lithology and tectonic setting in Table 3. How-
ever, these samples (n = 63) represent 10% of
the analyses considered by Plank and Lang-
muir [1998] in estimating global subducting
sediment (GLOSS). Loess is considered to be a
sediment type that perhaps best reflects the
upper crustal provenance for many elements
because of the relatively minor effects of
weathering [Taylor et al., 1983]. Accordingly,
several regional loess averages are given in
Table 4, and these are also plotted individually
on Figures 4±10.
[18] It is not possible to fully evaluate formal
statistical uncertainties for some of these aver-
ages because the primary sources do not provide
sufficient information on variance. However,
the large number of samples used to estimate
many of the averages coupled with the fact that
confidence in an average improves as a function
of the square root of the number of samples
results in relatively small uncertainties in the
averages (at 95% confidence level). For exam-
ple, Plank and Langmuir [1998] reported
standard deviations for the GLOSS data that
were typically 10±20% of the average for most
trace elements. Because of the very large num-
ber of samples used to formulate the average
(>500), this results in 95% confidence levels on
the means of 1±2%. At the other extreme, the
average river suspended sediment data have
relatively large standard deviations (25±50%
of the average values), probably a result of the
fact that these rivers sample upper crust of
widely varying tectonic settings and climatic
regimes. This coupled with the relatively small
 Geochemistry 3 mclennan: trace element composition and upper continental crust
Geophysics
Geosystems G
number of analyses (n = 7±19, depending on
element) results in 95% confidence limits on
the means of 10±30%. In the case of North
American shale composite (NASC), the data
represent a single analysis of a composite
sample, and analytical error likely dominates
the uncertainty.
4.1.1. Shales, muds, and loess (fine grain)
[19] Fine-grained sediment averages and com-
posites that are used are described below (see
Table 3). In estimating the average fine-grained
sediment, equal weight was given to each of the
various sediment composites and averages.
[20] 1. For the river suspended value, average
suspended sediment is from near the terminus
of 19 major rivers of the world that together
drain 13% of the exposed land surface [Mar-
tin and Meybeck, 1979; Gaillardet et al., 1999].
Not all elements are reported for all rivers with
the most extreme case being Sc (n = 7).
[21]2. Average loess is determined from the
mean of eight regional loess averages from
New Zealand, central North America, Kaiser-
stuhl region, Spitsbergen, Argentina, United
Kingdom, France, and China (see Table 4 for
sources; n = 52).
[22] 3. NASC is a composite of 40 sediments
(mainly shales), mostly from North America
[Gromet et al., 1984].
[23] 4. Post-Archean average Australian shale is
an average of 23 Australian shales of post-
Archean age [Nance and Taylor, 1976;
McLennan, 1981, 1989; Barth et al., 2000].
The original PAAS [Nance and Taylor, 1976]
reported REE data only; however, the remain-
ing elements were compiled by McLennan
[1981], and REE data were updated by McLen-
nan [1989]. Ta values used here were recently
reported by Barth et al. [2000].
2000GC000109
[24] 5. Average Russian shale is an average of
1.6 ± 0.55 Ga shales (4883 samples and 4
composites from 1257 samples) and 0.55±
0.0 Ga shales (6552 samples and 1674 com-
posites from 28,288 samples). Samples are
mainly from Russia and the former Soviet
Union but also include representative samples
from North America, Australia, South Africa,
Brazil, India, and Antarctica [Ronov et al.,
1988].
[25] 6. Average Phanerozoic cratonic shale is
from Condie [1993] (n > 100).
[26] 7. GLOSS is an estimate of the average
composition of marine sediment reaching sub-
duction zones, based on 577 marine sedi-
ments [Plank and Langmuir, 1998]. This
average differs from the other fine-grained
averages in that it includes a significant com-
ponent of nonterrigenous material, including
chemical sediment, pelagic sediment, and
coarser-grained turbidites. This leads to some
anomalies that are discussed below.
[27] 8. Average passive margin turbidite mud is
an average of modern turbidite muds from
trailing edges and the Ganges cone [McLennan
et al., 1990] (n = 9) and Paleozoic passive
margin mudstones from Australia [Bhatia,
1981, 1985a, 1985b] (n = 10).
[28] 9. Average active margin turbidite mud is
an average of modern turbidite muds from
active margins [McLennan et al., 1990] (n =
18) and average Australian Paleozoic turbidite
mudstones from oceanic island arcs (n = 9),
continental arcs (n = 12), and Andean-type
margins (n = 2) [Bhatia, 1981, 1985a, 1985b].
4.1.2. Sand and sandstones (coarse grain)
[29]Coarser-grained sediment averages that
were used are described below (see Table 3).
In estimating the average coarse-grained sedi-
 Geochemistry 3 mclennan: trace element composition and upper continental crust
Geophysics
Geosystems G
ment, equal weight was given to each of the
various sediment composites and averages.
[30] 1. Average tillite is derived from the average
of Pleistocene till from Saskatchewan [Yan et al.,
2000] (n = 33) and late Proterozoic tillite matrix
(texturally a sandstone) from Scotland [Panahi
and Young, 1997] (n = 21). A coarse-grained
glacial sediment average was included to be
comparable to the fine-grained loess deposits.
[31] 2. Average Phanerozoic cratonic sandstone
is from Condie [1993] (n > 100).
[32] 3. Average Phanerozoic greywacke is from
the mean of Paleozoic (n > 100) and Mesozoic-
Cenozoic (n > 100) averages [Condie, 1993].
[33]4. Average passive margin sand is an
average of modern turbidite sands from trailing
edges and the Ganges cone [McLennan et al.,
1990] (n = 11) and Paleozoic passive margin
sandstones from Australia [Bhatia, 1981,
1985b; Bhatia and Crook, 1986] (n = 15).
[34] 5. Average active margin sand is an aver-
age of modern turbidite sands from active
continental margins [McLennan et al., 1990]
(n = 25, with aberrantly high Cr and Ni from
one sample excluded) and average Australian
Paleozoic turbidite sandstones from oceanic
island arcs (n = 11), continental arcs (n = 32),
and Andean-type (n = 10) margins [Bhatia,
1981, 1985b; Bhatia and Crook, 1986].
4.2. Approach
[35] The approach adopted in this paper for
estimating upper continental crustal abundan-
ces of certain trace elements makes two basic
assumptions: (1) REE content of clastic sedi-
mentary rocks best reflects upper crustal abun-
dances and the upper crustal REE estimates of
TM85 are adopted (e.g., La = 30 ppm), and (2)
the sedimentary mass balance of the elements
2000GC000109
under consideration are dominated entirely by
clastic sedimentary rocks such that they have
low or negligible abundances in other sedi-
ments, such as pure carbonates, evaporites, or
siliceous sediments. In practice, this assump-
tion is more robust for some elements than
others (see section 6). Accordingly, by examin-
ing the relationship between a variety of trace
elements and REE (using the most incompat-
ible REE, La) in clastic sediments and sedi-
mentary rocks it is possible to evaluate upper
crustal La/element ratios. This approach is
similar to that used by McLennan et al.
[1980] to estimate upper crustal Th abundances
from the sedimentary record [also see McLen-
nan and Xiao, 1998].
[36] Clastic sedimentary data are divided into
``fine-grained'' lithologies, including shales,
muds, and silts (e.g., loess), and ``coarse-
grained'' lithologies, including sands, sand-
stones, and tillites, as described above. The
average composition of each lithology was
determined by giving equal weight to each of
the individual averages tabulated in Table 3.
The upper crustal La/element ratios were cal-
culated from the overall weighted average
composition, using the relative proportions of
shales (fine grained) to sandstones (coarse
grained) found in the geological record (shale/
sandstone ratio of 6), and thus taken to be
representative of average terrigenous sediment.
Finally, the upper crustal abundances were
determined from these La/element ratios,
assuming an upper crustal La content of 30
ppm (TM85).
[37] The uncertainties in this approach are
likely to be dominated by issues such as
weighting factors and representativeness of
samples rather than the statistical uncertainty
in the various sediment averages. As noted
above, the 95% confidence intervals for the
various sediment averages listed in Table 3 are
generally fairly small (mostly less than ‹10%).
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
On the other hand, some of these averages are
Upper Continental
based on only a few sedimentary sequences. Crust (TM85)
For example, the till average is from samples 100.0
Fine-grained

taken from only two sedimentary sequences, Coarse-grained

ppm / ppm Chondrites

and the active margin sand and mud averages
are largely based on relatively few sedimentary
sequences in Australia. Whether or not these
averages are representative of the various sedi-
mentary settings cannot be evaluated and is the 10.0
subject of further work.

[38] An additional potential source of uncer-

tainty is in the weighting factors used to
determine the fine-grained and coarse-grained
averages and overall averages. In calculating
(a)
the fine-grained and coarse-grained averages 1.0
an arbitrary weighting factor of 1 was given to Upper Continental
Crust (TM85)
each analysis listed in Table 3. In calculating 100.0
the overall average, the fine-grained and
Average Clastic Sediment
ppm / ppm Chondrites

coarse-grained averages were weighted to the

ratio of shale to sandstone in the geological
record. Although there is some uncertainty in
this ratio (e.g., see recent discussion by Lisitzin
[1996]), here I adopt the shale to sandstone
mass ratio of 6:1, which is approximately 10.0

midway between the average value measured

by a variety of workers (4.3:1; see Garrels and
Mackenzie [1971] for summary) and the theo-
retical value (7.1:1) calculated by Garrels and
Mackenzie [1971]. Because trace element
abundances in sandstones on average are sig-
nificantly less than those in shales and the La/
element ratios are generally similar (the great-
est difference, for La/Cs, is 50%), changing
the proportion of coarse-grained sediment by
as much as a factor of 2 has only a slight effect
(<5%) on the final upper crustal concentra-
tions.
(b)
1.0
La Ce Pr Nd SmEuGd Tb Dy Ho Er Yb
Figure 3. (a) Chondrite-normalized REE patterns
for various fine-grained and coarse-grained sedi-
ment averages and composites listed in Table 3
compared to upper crustal REE pattern from Taylor
and McLennan [1985]. (b) Comparison of weighted
average clastic sediment and upper crustal REE
patterns.

5. Results and compared with TM85 estimate of the upper

5.1. REE, Th, and Sc
[39] On Figure 3, the REE patterns of the
various averages and composites are plotted
continental crust. The long-standing observa-
tion that post-Archean sedimentary REE pat-
terns are remarkably uniform is apparent.
Although there is considerable variability in
 Geochemistry 3 mclennan: trace element composition and upper continental crust
Geophysics
Geosystems G
absolute abundances, mainly related to grain
size and dilution effects (e.g., quartz and car-
bonate), the general shapes of the patterns are
similar. The weighted average REE pattern has
somewhat elevated REE abundances compared
to the upper crustal estimate (10±15% on
100
2000GC000109
average), and this is expected because low
REE-bearing sedimentary lithologies, such as
carbonates and evaporites, have not been con-
sidered. The average sediment pattern is also
slightly less fractionated in light rare earth
elements (LREE) compared to the upper crustal
estimate, but the difference is not considered
large enough to warrant any revisions to the
upper crustal REE estimates.

[40] The upper crustal abundances of Th and Sc

by TM85 were estimated from the sedimentary
La (ppm)

data available at the time. Plots of La versus Th

and La versus Sc are shown in Figure 4. The
.8
h =2 sedimentary data scatter around the TM85
/T upper crustal La/Th ratio of 2.8. Although the
10 La
La/Sc ratios of the sediments are quite variable,
Coarse-grain
they also plot close to the TM85 upper crustal
Fine-grain ratio of 2.7. However, 11 of the 14 sediment
Loess averages plot at lower La/Sc ratio, and the
(a) weighted average of the sediment data has a
10 100 lower La/Sc ratio, averaging 2.2. This lower
Th (ppm) La/Sc ratio leads to a revised upper crustal Sc
100 abundance of 13.6 ppm, which is 24% higher
La/Sc=2.7
Sc=11ppm than that suggested by TM85 and essentially
identical to the estimate of Condie [1993]. This
revision also leads to a decrease in the upper
La (ppm)

crustal Th/Sc ratio from 1.0 to 0.8.

10
La/Sc=2.2
Sc=13.6ppm
(b)
10
Sc (ppm)
Figure 4. Plots of (a) La versus Th and (b) La
versus Sc for sediment averages and composites.
Circled cross and thick solid line represent upper
crustal abundances and La/element ratio of Taylor
and McLennan [1985]. Sediment data fall close to
the TM85 estimate of the upper crustal La/Th ratio.
Dashed line represents revised upper crustal La/Sc
ratio suggested by sedimentary data.
5.2. Rb and Cs
[41] TM85 estimated upper crustal Rb indi-
rectly from the sedimentary data by adopting
standard values for a series of canonical ratios
(Th/U, K/U, and K/Rb [also see McLennan et
al., 1980]). The weighted average La/Rb ratio
100
of clastic sediments, at 0.26 (Figure 5a), is
essentially identical to the TM85 upper crustal
La/Rb of 0.27. Although coarse-grained aver-
ages plot at systematically lower La/Rb com-
pared to TM85 upper crust, the fine-grained
averages plot at both lower and higher values.
Accordingly, the sediment data appear to pro-
vide direct confirmation of the upper crustal Rb
content estimated by TM85.
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
lower La/Cs ratios than the TM85 upper crustal
Coarse-grain value of 8.1. Coarse-grained sediment averages
Fine-grain
and some of the regional loess averages have
100 Loess
La/Cs that are higher than the TM85 upper
crustal value. Overall, 7 of the 10 sediment
La (ppm)

averages plot at higher La/Cs, and the weighted

average of the sediment data has La/Cs of 6.5
GLOSS
leading to an new upper crustal estimate of 4.6
ppm, which is 25% higher than the TM85
estimate.
7
0 .2
b=
/R 5.3. Nb, Ta, and Ti
10 La (a)
[43] Plots of La versus Nb, Ta, and Ti are
10 100
Rb (ppm) shown in Figure 6. As has been pointed out
100 by several authors, the sedimentary data have
uniformly lower Nb and Ta contents (i.e.,
La/Cs=8.1
higher La/Nb and La/Ta ratios) than the
Cs=3.7 ppm TM85 upper crustal estimate [Plank and
Langmuir, 1998; Barth et al., 2000]. The
La (ppm)

GLOSS sediment data evaluated here suggest an upper

La/Cs=6.5
Cs=4.6 ppm
(b)
10
1 10
Cs (ppm)
Figure 5. Plots of (a) La versus Rb and (b) La
versus Cs for sediment averages and composites.
Circled cross and thick solid line represent upper
crustal abundances and La/element ratio of Taylor
and McLennan [1985]. Sediment data fall close to
the TM85 estimate of the upper crustal La/Rb ratio.
Dashed line represents revised upper crustal La/Cs
ratio suggested by sedimentary data. Note that the
sediment average global subducting sediment
(GLOSS) plots at relatively low La/Rb and La/Cs
ratios. See text for discussion.
[42] On the plot of La versus Cs (Figure 5b) the
sediment data exhibit substantial scatter, but
with only one exception (GLOSS), the fine
grained sediment averages uniformly show
crustal La/Nb = 2.5 and La/Ta = 30.5, leading
to upper crustal estimates of Nb = 12 ppm and
Ta = 1.0 ppm, a reduction by half of those
values suggested by TM85, and further con-
firming the suggestions of Condie [1993],
Plank and Langmuir [1998], and Barth et al.
[2000].
[44] In contrast, La/Ti ratios are systematically
lower in clastic sediments than in the TM85
upper crustal estimate and suggest that the
average upper crustal Ti concentration should
be revised upward by 35% to 4100 ppm or
TiO2 = 0.68%. This estimate is somewhat less
than that suggested by Plank and Langmuir
[1998].
5.4. Ferromagnesian Trace Elements
(Cr, Ni, V, and Co)
[45] The data considered here confirm the
observation that fine-grained clastic sediments
typically have about twice the levels of
ferromagnesian trace elements compared to
the TM85 upper crustal estimates. Figure 7
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
plots La versus Cr and V as representative of
100 this group of elements. All sediment averages
La/Nb=2.5 plot at lower La/Cr and La/Ni (not shown)
Nb=12 ppm ratios, and all but two (coarse grained) sedi-
La (ppm)

ment averages plot at lower La/V and La/Co

(not shown) ratios. The weighted average of
the clastic sediment data suggests the follow-
ing upper crustal ratios: La/Cr = 0.36, La/V
La/Nb=1.20 = 0.28, La/Ni = 0.68, and La/Co = 1.8.
Nb=25 ppm
10 These ratios lead to proposed revisions to
the TM85 upper crustal values as follows: Cr
Coarse-grain
Fine-grain
= 83 ppm, V = 107 ppm, Ni = 44 ppm, and
Loess
(a)
Co = 17 ppm, approximately a factor of two
higher. Although absolute values differ in
10 100
detail (by 6±30%), these results confirm the
Nb (ppm) suggestion of generally higher ferromagnesian
100
trace elements in the upper crust by Condie
La/Ta=30.5
Ta=1.0 ppm
[1993].
La (ppm)

5.5. Other Elements (Zr, Hf, Ba, and Pb)

[46] No revisions to the TM85 upper crustal
La/Ta=13.6
Ta=2.2 ppm
estimates are indicated by the sedimentary data
10 for either Zr or Hf (Figure 8). The sedimentary
data scatter about the TM85 upper crustal La/
Zr and La/Hf ratios, and the weighted sedi-
mentary means predict concentrations within
(b) 10% of those of TM85. On average, coarse-
grained sediments plot at lower La/Zr and La/
1 10 Hf ratios than do fine-grained sediments, a
Ta (ppm) predictable consequence of heavy mineral
100 enrichments. It is of interest, however, that
the loess data also plot with, by far, the lowest
La/Ti=0.0100
Ti=3,000 ppm
La/Zr and La/Hf ratios of the fine-grained
sediments. This is consistent with the observa-
La (ppm)

tion of Taylor et al. [1983] that the aeolian

sedimentary transport processes involved with

Figure 6. Plots of (a) La versus Nb, (b) La versus

La/Ti=0.0074 Ta, and (c) La versus Ti for sediment averages and
Ti=4,100 ppm composites. Circled cross and thick solid line
10
(c) represent upper crustal abundances and La/element
ratio of Taylor and McLennan [1985]. Dashed line
1000 10000 represents revised upper crustal La/element ratios
Ti (ppm) suggested by sedimentary data.
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
tematics of clastic sediments (Figure 9), and
Fine-grain most data plot at the TM85 upper crustal La/Ba
Coarse-grain
100 Loess
ratio of 0.055. It is noteworthy, however, that
La/Cr=0.86
all of the fine-grained marine sediment aver-
Cr=35 ppm ages (GLOSS and turbidite muds from both
La (ppm)

active and passive settings) plot at systemati-

100
Fine-grain
Coarse-grain
Loess

La (ppm)
La/Cr=0.36
Cr=83 ppm
10
(a)
Avg. Loess
10 100

16
Cr (ppm)

0.
r=
/Z
La
10
100
La (ppm)

La/V=0.50 (a)
V=60 ppm
100 1000
Zr (ppm)

100

10
La (ppm)

La/V=0.28
V=107 ppm
(b)

10 100
V (ppm) Avg. Loess
2
5.
f=
/H

Figure 7. Plots of (a) La versus Cr and (b) La

La

versus V for sediment averages and composites.
Circled cross and thick solid line represent upper
crustal abundances and La/element ratio of Taylor
and McLennan [1985]. Dashed line represents
revised upper crustal La/element ratios suggested
by sedimentary data. Similar discrepancies are seen
for Ni and Co.
loess formation leads to significant heavy min-
eral enrichments.
[47] Similarly, no revision to upper crustal Ba
concentration is suggested by the La-Ba sys-
10
(b)
1 10
Hf (ppm)
Figure 8. Plots of (a) La versus Zr and (b) La
versus Hf for sediment averages and composites.
Circled cross and thick solid line represent upper
crustal abundances and La/element ratio of Taylor
and McLennan [1985]. Sediment data fall close to
the TM85 estimate of the upper crustal La/Zr and
La/Hf ratios. Note that loess falls at much lower La/
Zr and La/Hf ratios than do other fine-grained
averages. See text for further discussion.
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
100
value is also consistent with the various shield
Fine-grain
estimates (Table 1) that are all in the range of
Coarse-grain
La (ppm)

Loess
100
La/Pb=1.8
Pb=17 ppm

La (ppm)
Marine River
5 muds Suspended
05

10
0.
a=
/B
La

10

100 1000 La/Pb=1.5

Ba (ppm) Pb=20 ppm

Figure 9. Plot of La versus Ba for sediment (a)

averages and composites. Circled cross and thick 10 100
solid line represent upper crustal abundances and
La/Ba ratio of Taylor and McLennan [1985]. Pb (ppm)
Sediment data fall close to the TM85 estimate of
River Suspended Sediment
the upper crustal La/Ba ratio. Note that the fine- (Martin & Meybeck, 1979; Gaillardet et al., 1999)

grained marine muds have the lowest La/Ba ratios.

See text for further discussion. .5
b =1
/P
La (ppm)

100 La

cally lower La/Ba ratio than the other sediment

Da Hong Da
Garonne

averages. This is interpreted to result from

anomalously high Ba contents related to marine Seine

productivity and enrichments in pelagic sedi- Danube

ment [e.g., Francois et al., 1995]. Such sedi-

ment constitutes 1±2% of the sedimentary 10 (b)

record [e.g., Garrels and Mackenzie, 1971; 10 100

Lisitzin, 1996] and, accordingly, is likely to
have a relatively minor effect on the upper
crustal Ba estimate from the clastic sedimentary
record.
[48] The data for Pb do, however, indicate that a
modest decrease in upper crustal Pb abundan-
ces is warranted (Figure 10a), and nearly all
terrigenous sediment averages and composites
plot at a higher La/Pb ratio than the TM85
upper crustal estimate. These relationships sug-
gest that the upper crustal Pb concentration is
17 ppm, or a 15% decrease, a value also
proposed by Condie [1993]. This slightly lower
Pb (ppm)
Figure 10. (a) Plot of La versus Pb for sediment
averages and composites. Circled cross and thick
solid line represent upper crustal abundances and
La/Pb ratio of Taylor and McLennan [1985].
Dashed line represents revised upper crustal La/Pb
ratios suggested by sedimentary data. Note that
average suspended river sediment falls at much
lower La/Pb ratio and higher Pb content than do
other fine-grained averages. (b) Plot of La versus Pb
for suspended sediment from individual rivers
[Martin and Meybeck, 1979; Gaillardet et al.,
1999]. Note that some rivers with the highest Pb
content are those with a long history of industria-
lization. See text for further discussion.
Table 3. Selected Trace Elements for Estimates of Various Sediment Composites and Averages
Fine-Grained Clastic Sediment Averages Coarse-Grained Clastic Sediment Averages

Geosystems
Geophysics
Geochemistry
b c f g
Elements, River Loess NASC PAAS Russian Condie GLOSS PM AM Tillite j Condie Condie PM AM
ppm Suspendeda Shaled Shalee Mudh Mudi Sandstonek Greywackel Sandm Sandn
Sc 18.3 7.8 15 16 19.5 16 13.1 15.1 17.2 10.7 2.0 14 5.85 14.4
Ti 5520 3720 4200 6000 5100 4920 3720 4100 3860 2880 1500 4320 2360 3800
V 147 77


140 132 117 110 102 122 91 15 135 36 98

G
Cr 129 56 127 100 105 104 78.9 99 57 82 30 75 41 43

3 mclennan: trace element composition and upper continental crust

Co 18.9 10.6 26 20 21.5 20 21.9 15.5 14.5 10.7 2.5 18 6.5 13.5
Ni 62 20 58 60 57.5 54 70.5 54 25 36 8 38 19 16
Rb 113 73 125 160 144 163 57.2 235 141 80 25 90 61 67
Zr 191 302 200 210 213 201 130 168 155 167 105 147 285 155
Nb 17.1 12.7


18 14 15.4 8.94 14.2 9.7 9.4 4.0 10 7.71 6.73
Cs 8.84 3.8 5.2 6.0





3.48 4.78 5.57 2.6





1.42 2.57
Ba 635 458 636 650 677 551 776 823 646 476 150 625 403 441
La 43.3 27.9 32.0 38.2 33.5 38.8 28.8 33.0 26.1 25.7 10.3 28 27.2 20.7
Hf 5.77 8.9 6.3 5.0 6.6 4.6 4.06 5.45 4.96 4.37 3.1 3.8 9.68 4.73
Ta 1.39 0.92 1.12 1.28


1.4 0.63





0.61 0.30 0.83






Pb (73) 14.1


20 18.5 22 19.9 16.6 17.0 9.8 19 11 15.4 14.2
Th 14.7 8.6 12.3 14.6 12.8 13.5 6.91 15.0 13.8 8.4 4.2 8.8 11.0 9.2
a
Average river suspended load from 19 major rivers of the world [Martin and Meybeck, 1979; Gaillardet et al., 1999]. High Pb is likely due to pollution in several rivers.
b
Average loess based on eight regional averages (total n = 52); see Table 4 for sources.
c
North American shale composite based on composite of 40 shales of mainly Phanerozoic age [Gromet et al., 1984].
d
Post-Archean average Australian shale based on average of 23 Australian shales of post-Archean age [Nance and Taylor, 1976; McLennan, 1981, 1989; Taylor and McLennan, 1985;
Barth et al., 2000].
e
Average of Phanerozoic (n = 34,840) and late Proterozoic (n = 5940) shales mainly from Russia and former Soviet Union [Ronov et al., 1988].
f
Average post-Archean cratonic shale [Condie, 1993] (n > 100).
g
Average global subducting sediment [Plank and Langmuir, 1998].
h
Average passive margin turbidite mud derived from trailing edge and continental collision basins [McLennan et al., 1990] (n = 9) and average Paleozoic passive margin mud [Bhatia,
1981, 1985a, 1985b] (n = 10).
i
Average of active margin turbidite mud derived from average modern active margins[McLennan et al., 1990] (n = 18) and average Paleozoic oceanic island arc (n = 9), continental arc
(n = 12) and Andean-type margins (n = 2) [Bhatia, 1981, 1985a, 1985b].
j
Average tillite derived from late Proterozoic Port Askaig tillite matrix [Panahi and Young, 1997] (n = 21) and Pleistocene till from central Canada [Yan et al., 2000] (n = 33).
k
Average Phanerozoic cratonic sandstone [Condie, 1993] (n > 100).

2000GC000109
l
Average Phanerozoic greywacke, taken from mean of Paleozoic (n > 100) and Mesozoic ± Cenozoic (n > 100) averages [Condie, 1993].
m
Average post-Archean modern Trailing Edge and Continental Collision basins [McLennan et al., 1990] (n = 11) and Paleozoic passive margin sandstone from Australia [Bhatia,
1981, 1985b; Bhatia and Crook, 1986] (n = 15).
n
Average of active margin turbidite sand derived from modern active margin basins [McLennan et al., 1993] (n = 25) and average Paleozoic oceanic island arc (n = 11), continental arc
(n = 32), and Andean-type margins (n = 10) [Bhatia, 1981, 1985b; Bhatia and Crook, 1986].
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
Table 4. Regional Averages of Selected Trace Elements in Quaternary Loess
Element, New United Statesb Kaiserstuhlc Spitsbergend Argentinae United Franceg Chinah Average
a f
ppm Zealand Kingdom Loessi
Sc 8.1 5.3 5.85 11.9 7.8
Ti 3480 4020 1860 4140 4860 3420 4320 3770 3730
V 65 57 40 119 105 58 69 99 77
Cr 31 32 42 109 36 67 61 69 56
Co 9.6 5.6 6.5 14 14 9 8 18 10.6
Ni 13 12 24 24 16 20 17 34 20
Rb 83 74 47 80 79 73 61 89 73
Zr 366 420 255 278 234 327 357 181 302
Nb 12.7 15.0 9.8 14.3 10.1 11 10.5 11.7 12.7
Cs 3.8 2.8 1.9 3.9 5.0 2.9 6.5 3.8
Ba 572 681 195 554 578 332 298 457 458
La 35.4 34.3 25.0 29.3 23.9 19.7 24.9 30.4 27.9
Hf 10.4 13.5 6.8 4.8 8.9
Ta 1.12 1.03 0.76 0.93 0.80 0.87 0.92
Pb 13 14 4.2 17 18.3 15 13.2 18.0 14.1
Th 10.2 9.5 5.6 9.0 8.7 7 7.9 10.9 8.6
a
Average of five loess samples from Banks Penninsula, New Zealand [Taylor et al., 1983; Barth et al., 2000].
b
Average of four loess samples from Iowa and Kansas [Taylor et al., 1983; Barth et al., 2000].
c
Average of two loess samples from Kaiserstuhl region, Germany [Taylor et al., 1983; Barth et al., 2000].
d
Average of six loess samples from Spitsbergen [Gallet et al., 1998].
e
Average of seven loess samples from Argentina [Gallet et al., 1998].
f
Loess sample from United Kingdom [Gallet et al., 1998].
g
Average of seven loess samples from France [Gallet et al., 1998].
h
Average of 20 loess samples from China [Taylor et al., 1983; Gallet et al., 1996; Jahn et al., 2001].
i
Average Loess estimated from average of New Zealand to China values.

Pb = 14±18 ppm. Of note is the exceptionally
low La/Pb ratio of average suspended river
sediment (Figure 10a). This is due mainly to
exceptionally high Pb concentrations in sedi-
ment from several rivers that in some cases are
draining regions with a long history of indus-
trialization (Figure 10b), suggesting that pollu-
tion may have a significant effect on the Pb
content of suspended sediment in at least some
modern rivers.
6. Discussion
6.1. Some Comparisons
[49]The upper crustal abundances of K, U, and
Rb have been estimated indirectly on the basis
of the clastic sedimentary record, using ratios
such as Th/U = 3.8, K/U = 10,000, and K/Rb =
250 [McLennan et al., 1980; TM85]. Since no
change to Th is indicated from the analysis of
sedimentary data presented in this paper, like-
wise no revisions to K, U, and Rb are sug-
gested. It is of note that in this study Rb also is
estimated directly from the sedimentary record,
using La/Rb ratios, and the Rb value obtained
agrees with the indirect estimate to within 4%
and agrees with the average shield surface to
within 12%.
[50] The upper crustal TM85 Cs content of 3.7
ppm was determined indirectly from Rb = 112
ppm and an assumed upper crustal Rb/Cs ratio
of 30. On the basis of sedimentary rocks,
McDonough et al. [1992] suggested an upper
crustal Rb/Cs of 19 and Cs content of 6
ppm (both with large suggested uncertainties),
and Plank and Langmuir [1998] implied a ratio
as low as 15.3 from a Cs content of 7.3 ppm.
The large amount of sedimentary data consid-
 Geochemistry 3 mclennan: trace element composition and upper continental crust
Geophysics
Geosystems G
ered in this study suggests an upper crustal Rb/
Cs ratio of 24. This ratio is likely to be a
lower limit because the larger Cs ion would be
expected to be held preferentially over Rb onto
clay minerals [e.g., Dupre et al., 1996], leading
to low Rb/Cs ratios in the finest-grained sedi-
ment, and excluded preferentially over Rb from
Ca- and Na-bearing carbonate and evaporite
minerals [e.g., Okumura and Kitano, 1986],
leading to high Rb/Cs ratios in the nonclastic
parts of the sedimentary record (see further
discussion in section 3.1).
[51] The high upper crustal Cs content esti-
mated by Plank and Langmuir [1998] may in
fact be an artifact of their approach, where Cs
was estimated from a correlation between Rb
and Cs in marine sediments and upper crustal
Rb content was taken from TM85. From Table
3 it can be seen that the average subducting
sediment (GLOSS in Table 2) in fact has a
relatively low Cs content compared to any of
the other fine-grained sediment averages and is
rather similar to the TM85 upper crustal esti-
mate. However, GLOSS also has a much lower
Rb content than most of the other fine-grained
sediment averages and more than a factor of 2
lower than the upper crustal Rb estimate of
TM85. The overall effect is that the La/Rb ratio
of GLOSS is the highest of any of the sediment
averages, whereas the La/Cs ratio of GLOSS
falls within the range of the other fine- and
coarse-grained sediment averages (Figure 5).
Accordingly, the marine sedimentary record
studied by Plank and Langmuir [1998] appears
to be characterized by anomalously low Rb
content rather than high Cs content, and the
high estimate of upper crustal Cs abundances is
probably an artifact of this anomaly.
[52]The values for Nb and Ta obtained in this
study are essentially identical to those sug-
gested by Plank and Langmuir [1998] and
Barth et al. [2000]. The values of TM85 were
based on the Canadian Shield Nb estimate of
2000GC000109
Shaw et al. [1976] and an upper crustal Nb/Ta
of 11.6 [from Wedepohl [1977]; however, all
other shield areas that have been examined
have lower Nb by a factor of >2 on average
(Table 1), and accordingly, the lower estimates
also appear consistent with the surface sam-
pling of shields.
[53] The proposed increases in the ferromagne-
sian trace elements Cr, V, Ni, and Co average
about a factor of 2 greater than the TM85
values and are most similar to, although gen-
erally lower than, the upper crustal estimates of
Condie [1993]. The TM85 values were essen-
tially identical to the Canadian Shield estimates
(see Table 1). In general, the various shield
estimates are highly scattered for these ele-
ments (Table 1), but the ferromagnesian trace
elements proposed here are slightly higher than
the shield average.
6.2. Implications for the Bulk
Continental Crust and Lower Crust
[54] In the model of crustal composition pro-
posed by TM85 the lower crustal composition
is derived by assuming the upper crust con-
stitutes 25% of the total continental crust.
Accordingly, any revision to upper crustal
abundances has an effect on estimates of the
lower continental crust.
[55] In the case of Cs, this leads to difficulties in
that the elevated upper crustal Cs proposed here
(Cs = 4.6 ppm) when combined with the bulk
crustal estimate of TM85 (Cs = 1.0 ppm)
creates mass balance difficulties for the lower
crust, assuming it constitutes 75% of the
total. Accordingly, the bulk crustal abundances
of the most incompatible elements (Cs, Rb, K,
Th, and U) require reevaluation [McLennan et
al., 2001]. McLennan and Taylor [1996] sug-
gested that the continental heat flow data were
consistent with slightly higher bulk crustal
abundances for K, Th, and U compared to
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
Table 5. Composition of the Continental Crust Revised From Taylor and McLennan [1985]
Element Upper Crust Bulk Crust Lower Crust

Li, ppm 20 13 11
Be, ppm 3.0 1.5 1.0
B, ppm 15 10 8.3
Na, wt % 2.89 2.30 2.08
Mg, wt % 1.33 3.20 3.80
Al, wt % 8.04 8.41 8.52
Si, wt % 30.8 26.8 25.4
P, ppm 700






K, wt % 2.80 1.1a 0.53a
Ca, wt % 3.00 5.29 6.07
Sc, ppm 13.6b 30 35b
Ti, wt % 0.41b 0.54 0.58b
V, ppm 107b 230 271b
Cr, ppm 83b 185 219b
Mn, ppm 600 1400 1700
Fe, wt % 3.50 7.07 8.24
Co, ppm 17b 29 33b
Ni, ppm 44b 128 156b
Cu, ppm 25 75 90
Zn, ppm 71 80 83
Ga, ppm 17 18 18
Ge, ppm 1.6 1.6 1.6
As, ppm 1.5 1.0 0.8
Se, ppm 50 50 50
Rb, ppm 112 37c 12c
Sr, ppm 350 260 230
Y, ppm 22 20 19
Zr, ppm 190 100 70
Nb, ppm 12b 8.0b 6.7b
Mo, ppm 1.5 1.0 0.8
Pd, ppb 0.5 1 1
Ag, ppb 50 80 90
Cd, ppb 98 98 98
In, ppb 50 50 50
Sn, ppm 5.5 2.5 1.5
Sb, ppm 0.2 0.2 0.2
Cs, ppm 4.6c 1.5c 0.47c
Ba, ppm 550 250 150
La, ppm 30 16 11
Ce, ppm 64 33 23
Pr, ppm 7.1 3.9 2.8
Nd, ppm 26 16 12.7
Sm, ppm 4.5 3.5 3.17
Eu, ppm 0.88 1.1 1.17
Gd, ppm 3.8 3.3 3.13
Tb, ppm 0.64 0.60 0.59
Dy, ppm 3.5 3.7 3.6
Ho, ppm 0.80 0.78 0.77
Er, ppm 2.3 2.2 2.2
Tm, ppm 0.33 0.32 0.32
Yb, ppm 2.2 2.2 2.2
Lu, ppm 0.32 0.30 0.29
Hf, ppm 5.8 3.0 2.1
Ta, ppm 1.0b 0.8b 0.73b
W, ppm 2.0 1.0 0.7
 Geochemistry 3 mclennan: trace element composition and upper continental crust 2000GC000109
Geophysics
Geosystems G
Table 5. (continued)
Element Upper Crust Bulk Crust Lower Crust
Re, ppb 0.4 0.4 0.4
Os, ppb 0.05 0.05 0.05
Ir, ppb 0.02 0.1 0.13
Au, ppb 1.8 3.0 3.4
Tl, ppb 750 360 230
Pb, ppm 17b 8.0 5.0b
Bi, ppb 127 60 38
Th, ppm 10.7 4.2a 2.0a
U, ppm 2.8 1.1a 0.53a
a
Revisions suggested by McLennan and Taylor [1996].
b
Revisions suggested in this study.
c
Revisions discussed in this study and by McLennan et al. [2001].

those suggested by TM85 and proposed K =
1.1%, Th = 4.2 ppm, and U = 1.1 ppm.
Maintaining a bulk crustal K/Rb ratio of
300, this also suggests that the bulk crustal
Rb content should be revised slightly upward to
37 ppm. The bulk crustal TM85 Cs estimate
came from an assumed crustal Rb/Cs ratio of
30. The bulk crustal composition of TM85 is
based to a large degree on Archean crustal
compositions, but there are in fact very few
high-quality Cs data for Archean rocks. For
example, Cs data are absent from the most
recent compilation of Archean igneous rock
compositions [Condie, 1993]. If the average
island arc volcanic rock Rb/Cs of 25 is adopted
instead (from Taylor and McLennan [1985];
note McDonough et al. [1992] obtained the
same bulk crust Rb/Cs ratio using a different
approach), this leads to a revised bulk crustal
Cs content of 1.5 ppm, a value adopted here.
Note that this Rb/Cs ratio is also very close to
the clastic sedimentary Rb/Cs ratio of 24,
discussed above. These revisions result in
lower crustal abundances of Cs = 0.47 ppm
and Rb = 12 ppm.
[56] In calculating the Nb and Ta abundances of
the bulk crust, Taylor and McLennan [1985]
relied on average Phanerozoic island arc vol-
canics because there were few relevant data
from Archean rocks. This situation has
changed, and recently, Condie [1993] compiled
Nb and Ta concentrations for the dominant
Archean igneous lithologies. For the model
proposed by TM85 these data suggest a slight
downward revision of bulk crustal abundances
for these elements, such that Nb = 8 ppm and
Ta = 0.8 ppm, resulting in calculated lower
crustal abundances of Nb = 6.7 ppm and Ta =
0.73 ppm. In Table 5, all of the revisions to the
crustal abundances of TM85 that are suggested
here as well as by McLennan and Taylor [1996]
and McLennan et al. [2001] are summarized.
Acknowledgments
[57] I am grateful to G. Xiao for assistance in compiling
Rb-Cs data in sedimentary environments and to Ross
Taylor for providing some unpublished Cs data and for a
continuing discussion on crustal composition. I also thank
Kent Condie, Bill McDonough, Roberta Rudnick, Hubert
Staudigel, Bill White, and an anonymous reviewer for
comments.
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