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Estimations of Clarkes for Carbonaceous biolithes: World averages for trace

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International Journal of Coal Geology 78 (2009) 135–148

Contents lists available at ScienceDirect

International Journal of Coal Geology

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

Estimations of Clarkes for Carbonaceous biolithes: World averages for trace element
contents in black shales and coals
M.P. Ketris, Ya.E. Yudovich ⁎
Institute of Geology, Komi Scientific Center, Ural Branch of the Russian Academy of Sciences, 167023 Syktyvkar, Morozova st., 100, ap. 49, Russia

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

Article history: Black shale and coal Clarke values are the average trace element contents in the World black shales and coals.
Received 27 October 2008 These calculations are made in Russian geochemistry but up to now are poorly known in the West.
Received in revised form 1 January 2009 Modern tables of black shale and coal Clarkes are presented, based on comprehensive calculations using very large
Accepted 6 January 2009
amount of information (thousands analyses of black shales, coals, and coal ashes for trace elements). In black shale
Available online 14 January 2009
geochemistry, three figures were calculated for each main lithologies: terrigenous (+tuff), chert, and carbonate.
Keywords:
Two Clarke estimations are presented, named “lithological” (K1) and “lithostratigraphical” (K2). In coal
Metalliferous black shales geochemistry, seven figures were calculated for each trace element: average content in hard coals and their
Coal ashes; average content in brown coals and their ashes; average content in all coals and their ashes; and coal
Geochemistry affinity index (or “coalphile index”) = average content in all ashes/Clarke values of sedimentary rocks.
Trace elements The black shale and coal Clarkes presented here provide an important scientific base for many geochemical
World average contents (black shale and coal comparisons and issues.
Clarke values) © 2009 Elsevier B.V. All rights reserved.

1. Introduction 1.2. Some history

In 1923, the famous Russian geochemist A.E.Fersman1 introduced the
term “clark” (= Clarke, in English), in honor of the prominent American
scientist, one of the founders of geochemistry, F.W.Clarke (who worked
many years as Chief Chemist at U.S. Geol. Survey), who first calculated
average composition of various rocks, and later, the Earth's crust.
1.1. Meaning of the Russian term Clarke
Fersman defined “Clarke” as the average content of given chemical
element in the Earth's crust and also in the hydrosphere. This term very
soon took root in Russian literature, but, up to now, is nearly unknown
to Western researchers2. With time, however, a sense of the term was
strongly extended: many other geochemical averages were named as
“Clarkes”, for example, “Clarkes of granites”, “Clarkes of basalts”,
“Clarkes of sedimentary rocks”, etc., including “coal Clarkes”, i.e.
average trace element contents in the World coals. For example, coal
Clarke of Ge is 3.0 ± 0.3 ppm (hard coals) and 2.0 ± 0.2 ppm (brown
coals) (Yudovich and Ketris, 2004).
⁎ Corresponding author. Tel.: +7 821 31 19 24.
E-mail addresses: yudovich@geo.komisc.ru, EYuYa@yandex.ru (Y.E. Yudovich).
1
Fersman was the first, who gave a lecture course “Geochemistry” (Moscow, 1912).
Later, he created many fundamental proceedings on geochemistry, for example,
“Pegmatites” (1931), “Geochemistry” (4 volumes, 1933–1939), etc.
2
That is why, in our articles in As or Hg in coal (Yudovich and Ketris, 2005a,b), the
terms like “coal Clarke of As” need obligatory the special explanation for the Western
reader.
In black shale geochemistry, a well-known estimation of average
contents of trace elements in black shales was made by Vine and
Tourtelot (1970). Their calculations, using 20 U.S. Phanerozoic black
shale units, have been widely cited (by many researchers) because
there were no other estimations.
But, it is desirable to use more comprehensive world-wide data for
more accurate conclusions. Our calculations are based on tens of
thousands of analyses employing hundreds of sample mean values.
Statistical processing of the data supported new Clarke estimations
which seem to be more plausible.
In coal geochemistry, there are known some attempts to calculate
coal Clarkes for several trace elements. The first calculations were
made by the Norwegian-German geochemist, another founder of
geochemistry3, Goldschmidt (1935), at start of the 1930s. Goldschmidt
organized systematical analyses of some European coals for trace
elements, using modern (for that time) analytical methods – emission
spectrographic and X-ray fluorescence analyses. Goldschmidt's esti-
mations of trace element average contents for “ordinary” (common)
and “enriched” coal ashes were, for many consequent years, the
“compass” for geochemists dealing with coal.
Later, we find some averages in studies by Krauskopf (1955) and
Bethell (1962). The first wide (including most trace elements and most
3
Two other founders of geochemistry, new science of 20th century, were Russian
scientists, V.I.Vernadski and his follower, A.E.Fersman.

0166-5162/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2009.01.002
 Author's personal copy
136 M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148
Fig. 1. Structure of the scientific field in black shales geochemistry. The areas with neighboring overlaps are shaded (Yudovich and Ketris, 1994, p. 4; 1997, p. 5).
World coals) calculation of coal Clarkes was performed in the USSR
(Yudovich et al., 1972). Later, Valkovič's (1983a,b) estimations (based
on U.S. figures, but including some others) were developed.
Valkovič (1983a,b) used frequency histograms for statistical
evaluations of averages. It is a very useful working procedure, and it
was independently widely used in our new calculations (Yudovich
et al., 1985). The estimations based on thousands of analyses, were
made as four figures for each trace element: (1, 2) for hard coals and
their ashes, and (3,4) for brown coals and their ashes. These new coal
Clarke figures (with detailed explanation of stepped calculation
procedure), were cited in Russian, East European, Indian, and Chinese
studies for many years.
Unfortunately, it was in a Russian-language book, and for this
reason, our figures remained practically unknown to the most
Western researchers. Swaine (1990) published his excellent outline
on trace elements in coal. He tried to embrace all the World coals, but
his outline had large omissions of the East (Soviet) Block coals. It is of
note, Swaine's world estimation were, as a rule, rough interval values;
for example, as 10–40 ppm (and not, say, as 16 ± 5 ppm, where ±5 ppm
means statistical standard deviation).
In last decades of 20th century, great changes appeared in coal
geochemistry due to environmental problems caused by wider
consumption of coal in electric power plants. This enlarged demand
for coal created abundant new geochemical studies, with analyses of
coal on toxic elements, such as Be, Hg, Cd, Pb, As, Sb, Se, Cr, Mn, U, and
some others. In addition, coal mining sharply increased in developing
countries, such as Spain, Turkey, Greece, China, India, Brazil, Peru, and
Nigeria, among others. These coals have been analyzed using wide
international cooperation, for example, with U.S. Geological Survey,
using modern analytical equipment.
Therefore, the amount of coal-trace-element figures has greatly
increased. The U.S. Geological Survey created their “Coal Quality
(COALQUAL) Database” (Bragg et al., 1998), with more than 13,000
analyses for most trace elements. Finally, in recent decades, due to
mostly Russian researchers (V.V. Seredin, S.I. Arbuzov and some
others), the old problem became again actual: coal as industrial
resource of trace elements (Sc, Ge, REE, Nb, Ta, Re, Au, and platinum
group elements, PGE) (Arbuzov et al., 2000, 2003; Zharov et al., 1996;
Seredin and Shpirt, 1995; Seredin and Finkelman, 2008).
All the latter work necessitates new coal Clarkes calculation.
2. Estimation of trace elements Clarkes for black shales
The so called “black shales” (sedimentary rocks enriched in Corg)
are of great interest to geochemists, lithologists, paleontologists,
mineralogists, ore prospectors, and oil geologists, chemists, and
technologists in the field of oil shale industry (Fig. 1).
For a geochemist, black shales are anomalous rocks enriched in P,
U, Mo, V, Re, Se, Zn, Hg, and some other trace elements. For a
lithologist, they are unusual sedimentary rocks, mixtures of organic
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M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148
and inorganic matter at varying ratios. The inorganic matter may be of
almost any composition: clay, silt, sand, carbonate, chert, phosphate,
tuff, and may be deposited in nearly any facies. For a stratigrapher and
paleontologist, in general, black shales present special stages in the
history of sedimentary shell. For an ore prospector, black shale (or oil
shale) species are the most likely oil-productive source beds. Finally,
so called oil shales are also black shales containing “shale oil”, which
can be extracted by means of pyrolysis. World “oil shale” reserves
exceed petroleum reserves.
All the topics above mentioned account for abundant references on
black shale (and oil shale) geochemistry and geology. Many scientific
congresses, symposiums, and workshops took place on these
problems. For example, a symposium “Geochemistry, Mineralogy
and Lithology of Black Shales” was held in 1987 in Syktyvkar (Russia)
under the direction of the second author. Of special note was the
UNESCO International Geological Correlation Program Project 254,
entitled “Metalliferous Black Shales”.
As a result, two of our Russian monographs were published
(Yudovich and Ketris, 1988, 1994), and also short English outline with
huge bibliography (Yudovich and Ketris, 1997). In the 1994-mono-
graph, Clarke estimations for more than 60 trace elements in black
shales were first calculated. Such calculations are difficult because of
lithological diversity of black shales, among other reasons.
Fig. 2. Common median calculation (± standard deviation, shaded column): the example is for uranium in black shales (Yudovich and Ketris, 1994, p. 44; 1997, p. 31). Each point
represents one “primary statistical sample”. Q1 and Q2 are first and third quartilies of frequency distribution. Black shale lithologies: 1 – carbonate, 2 – clay, 3 – silt and sand, 4 – chert,
5 – tuff, 6 – phosophate, 7 – shale of unclear lithology.
137
2.1. An “ideal” information file
Such a file should include answers to the following questions:
- where were the samples taken from?
- what is the correct name of the rock?
- what is the correct stratigraphic position of the rock samples?
- what are the analytical errors and accuracy?
- how many rock samples were analyzed?
Such informational “ideal” is hardly achievable in most cases; as a
rule, some information is not available in literature. As an example,
information about Corg content was often lacking, although it is crucial
for geochemical conclusions. As there are no Corg data, rough Corg
estimation may be made using chemical analysis data (Yudovich and
Ketris, 1988, p. 29).
2.2. Calculation method
All calculation procedures may be divided into several stages
(Yudovich and Ketris, 1994):
1) formation of so called “primary statistical samples”; 2)
calculation of common median and its standard deviation; 3)
estimation of geochemical background and geochemical anomalies;
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138 M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148
4) formation of so-called “second statistical samples”; 5) “lithological
Clarke K1” estimation; 6) “lithostratigraphic Clarke K2” estimation.
2.2.1. “Primary statistical samples” and common median calculations
As a base (the “elementary unit”) for calculations, “a primary
sample” was used. The primary sample is a group of analyses of
lithologies representing to certain stratigraphic unit of some region.
For example: “Lower Carboniferous (=Mississippian) black cherts of the
Pai-Khoi”. We dealt with two different situations.
First: primary samples were already available from the literature as
average values. Such samples were sometimes heterogenous; for
instance, “carbonates + claystones”, although such rocks are known to
widely differ in trace elements content. Further, some data recorded in
Soviet references were average values for entire sedimentary
sequences, the so called “carbonaceous formations” (Sozinov et al.,
1988).4 The term itself is not clearly defined and the averages cannot
geochemical applications.
Second: primary statistical samples were not found in the
literature, but analyses were available for statistical processing.
Recalling the above mentioned information about geological age,
lithologies etc., the primary sample averages may be obtained. Given
considerable data dispersion, we applied mean median calculations,
while at small dispersions simple arithmetic means were calculated.
Then “common medians” were graphically estimated. Each point
of such graph represents one primary sample mean. The points are
plotted on horizontal lines representing a certain stratigraphic level
each (Fig. 2).
The following step is a common median standard deviation
calculation:
pffiffiffiffiffi
δMe = ðQ3 − Q1 Þ=2 N; ð1Þ
where:
- N is number of points (=primary samples),
- Q1 and Q3 are the first and the third quartiles of frequency
distribution.
The median was tabulated in the form of Me ± δMe. The standard of
the primary frequency distribution, δx, was calculated as:
δx = Q3 − Me
The geochemical background value (GB) is a frequency distribution
part limited by the first and the third quartiles:
GB = Q3 − Q1
Hence, 50% of primary sample means constitute a geochemical
background. Positive geochemical anomalies (A) are determined by
adding standard deviations to the common median:
A0 = Q3 = Me + 1δx ðqanomalyqÞ
A1 = Q3 + 1δx = Me + 2δx ðqstrong anomalyqÞ
A2 = Q3 + 2δx = Me + 3δxðqvery strong anomalyqÞ
Common median and quartiles values allow estimation of “true”
element distribution in black shales. The median is particularly con-
4
It is necessary to note, that the term “formation” in Russian geological literature
has a different meaning than in the West. “Formations” as understood in Russia are
nearly equal to “assemblages”; they denote much thicker stratigraphic units than
implied by American usage. What is meant by “formation” in the USA is close to
“member” in Russia (“sveeta” or свита in Russian).
venient because its value is little influenced by individual extreme
values, when a data population is large enough.
It is clear, however, that common median cannot be used for Clarke
estimations because it is dependent on the available set of data. Some
black shales have been studied in detail and described in numerous
geochemical publications. Others, on the contrary, are poorly known,
hence they are represented only as few points (=primary samples
means) on the graphs. For this reason, the common median value is
more affected by better studied black shales than by less studied ones.
A good example is Goldschmidt's reports on average values for
West Europian coals. They had been cited for a long time as Clarke
values for coals worlwide. But, as was subsequently shown, the
average values proved inflated since geochemistry of West European
coals is sharply anomalous (Yudovich et al., 1985).
2.2.2. “Second statistical samples” and “lithostratigraphic subclarkes”
The following calculation step is averaging primary sample means
belonging to a given age, region, and lithology. Several primary
samples thus grouped make up a “secondary sample”, giving an
opportunity to calculate “lithological subclarkes”. Unfortunately,
scantiness of lithological information, typical for many geochemical
reports, brought us to employ it in a very rough form: lithologies were
restricted to the following three: carbonates, cherts, and terrigenous
rocks, even without classifying the latter into clastic and clayey ones.
The rocks of volcanic-sedimentary origin were grouped within one of
the three types, more, however, with terrigenous rocks. Phosphate
rocks needed to be distinguished for some elements (P, Sr, U).
“Lithological subclarkes” were calculated for the following strati-
graphic levels:
1. Recent + Holocene
2. Paleogene + Neogene
3. Cretaceous
4. Jurassic
5. Triassic + Permian
6. Carboniferous (Mississippian + Pennsylvanian)
7. Devonian
8. Silurian
9. Ordovician
10. Cambrian
ð2Þ
11. Vendian
12. Riphean = Upper Precambrian
13. Karelian (Aphebian) = Middle Precambrian
14. Upper Archean and 15. Lower Archean = Lower Precambrian
ð3Þ These 15 units constitute four larger stratons: Phanerozoan
(including Vendian, or “Eocambrian” according to Salop, 1982),
Upper, Middle, and Lower Precambrian.
It is necessary to average the means of the litologies (=second
statistical samples) in order to obtain “lithostratigraphic subclarkes”.
ð4Þ For example, data set named “Carboniferous Black Shales” consists of:
two carbonate samples (20 analyses),
five chert samples (143 analyses),
ð5Þ 19 terrigenous (+volcanic-sedimentary) samples (950 analyses).
Obviously, calculation of arithmetic mean by lithologies would be
incorrect since of Carboniferous subdivisions are different in thick-
ð6Þ ness. Hence, straton means must be “weighted” for abundance of
lithologies. For weight coefficients we used values recommended by
A.I. Yeliseev (1997, oral communication)5:
cherts : carbonates : terrigenous rocks = 0:2 : 0:3 : 0:5 ð7Þ
5
These values are based on an extended study of the Russian plate/the Urals
boundary zone [Eliseev, 1978, 1982; Puchkov, 1979].
 Author's personal copy
M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148
If phosphate rocks are present, carbonates make up 0.29 and phos-
phates 0.01.
For example, mean Zn contents for Carboniferous carbonates,
cherts, and terrigenous rocks make up 440, 400, and 160 ppm
respectively. As a result, the weighted mean for Carboniferous black
shales (“lithostratigraphic subclarke”) may calculated as follows:
K2 ðCarboniferousÞ = 0:3 × 440 + 0:2 × 400 + 0:5 × 160 = 280 ppm:
2.2.3. “Lithological Clarke K1” estimation
Having lithologic averages for each straton (for example, “mean Zn
content in Carboniferous cherts”), one may calculate “common
lithological Clarke K1” as shown in Fig. 3, left.
First, lithologic subclarkes are calculated using 15 (or fewer)
stratons (i is a straton's number):
 
K1 ðCaÞ½carbonate rocks = Median KiCa
 
K1 ðSiÞ½cherts = Median KiSi
 
K1 ðAlÞ½terrigenous + volcanicsedimentary rocks = Median KiAl ð11Þ
Second, “lithological Clarke K1” is calculated as a weighted mean:
K1 ¼ 0:2K1 ðSiÞ þ 0:3K1 ðCaÞ þ 0:5K1 ðAlÞ
In this type of calculation, preference is given to black shale
lithologies; in spite of uncertainty in rock names, the Clarke values
obtained provide comparisons which arrive at unexpected conclu-
sions. For example, for Zn we have:
K1 ðCaÞ ¼ 140  43; K1 ðSiÞ ¼ 160  30; and K1 ðAlÞ ¼ 140  20 ppm:
Similar subclarke values for Zn in chert and carbonate black shales
indicate mostly hydrogenic Zn-origin. Moreover, enriched Zn content
Fig. 3. Calculation of the qlithologicalq and qlithostratigraphicq Clarkes K1 and K2 (Yudovich and Ketris, 1994, p. 47; 1997, p. 34). See the text for comments.
139
in black cherts has untrivial implications suggesting its biogenic origin
(Yudovich and Ketris, 1994, 1997).
2.2.4. “Lithostratigraphic Clarke K2” estimation
First, stratone subclarkes are grouped as follows:
ð8Þ K1(Ph) – for Phanerozoic including Vendian, mean of 11 stratones;
K1(pЄ3) – for Upper Precambrian (=Riphean);
K1(pЄ2) – for Middle Precambrian (=Karelian);
K1(pЄ1) – for Lower Precambrian, mean of two stratons.>
Second, “lithostratigraphic clarke K2” is calculated by averaging the
values:
K2 ¼ 1=4½K1 ðPhÞ þ K1 ðpЄ3 Þ þ K1 ðpЄ2 Þ þ K1 ðpЄ1 Þ ð14Þ
ð9Þ
The procedure is aimed at considering the relative duration of
ð10Þ
geochrones, consequently, to some extent, corresponding black shale
masses for each straton. It is obvious that K2 is 75% composed of pre-
Phanerozoan stratons (3:1), whereas, for K1 estimations the correspond-
ing ratio is 4:11. This is why, K2-values strongly depend on old
metamorphic schists subclarkes. If the schists are enriched in any element
as compared with Phanerozoan, K2-values will be higher than K1 and vice
ð12Þ versa. Besides, if qtrueq black shale distribution in the sedimentary shell is
different from 3:1, K2-estimation would be also invalid.
2.3. Some words about “true” Clarkes
It is hard to say which of the estimations, K1 or K2, is more relevant.
For this reason both the estimations are tabulated (see Tables 1 and 2).
ð13Þ
The closer are K1 and K2 values, the more reliable is the “true”
Сlarke value, which is a mathematical expectation of a random value.
Besides, similar K1, K2 and common median values are an important
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140 M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148

Table 1
Some statistics of trace elements distribution in black shales, ppm

Elements N n Me ± δMe Geochemical background A0 A1 K1 ± δK1 K2 KCa

1 ±δ KSi
1 ±δ KAl
1 ±δ

Typical cation-forming lithophiles

Rb 80 5790 74 ± 4 40–120 120–170 170–200 68 ± 5 76 39 ± 4 44 ± 6 93 ± 9
Li 57 4520 31 ± 2 15–50 50–70 70–100 33 ± 3 37 24 ± 10 19 ± 2 44 ± 2
Cs 33 3170 4.7 ± 0.4 2–7 7–10 10–12 4.8 ± 0.6 4.2 4.1 ± 0.8 3.0 ± 1.6 5.9 ± 1.0
Tl 18 2710 2.0 ± 0.9 0.5–10 10–15 15–25 2.5 ± 0.7 2.2 0.7 ± 0.8 4.8 ± 2.1 2.6 ± 1.1
Sr 304 16650 190 ± 10 100–300 300–400 400–500 290 ± 10 230 480 ± 40 140 ± 20 200 ± 10
Ba 314 15100 500 ± 20 270–800 800–1000 1000–1400 590 ± 40 630 540 ± 90 740 ± 70 560 ± 60

Cation- and anion-forming lithophiles with constant valency

Be 127 7810 2.0 ± 0.1 1–3 3–4 4–5 2.1 ± 0.1 2.6 1.6 ± 0.4 2.2 ± 0.2 2.4 ± 0.2
Sc 140 6880 12 ± 1 7–20 20–25 25–30 11 ± 0.5 12 5.9 ± 0.5 11 ± 1.1 14 ± 1
Y 142 8620 26 ± 1 15–40 40–50 50–65 23 ± 1 23 12 ± 3.4 25 ± 2 29 ± 1
Yb 110 5640 2.8 ± 0.1 2.0–3.5 3.5–4.0 4.0–5.0 2.6 ± 0.1 2.8 1.7 ± 0.2 2.9 ± 0.2 2.9 ± 0.2
La 128 4495 28 ± 1 20–40 40–50 50–60 28 ± 2 26 22 ± 2 29 ± 1 31 ± 2
Ce 75 2800 58 ± 3 35–80 80–110 110–130 58 ± 6 55 50 ± 12 53 ± 22 61 ± 6
Eu 40 1500 1.2 ± 0.04 1.0–1.4 1.4–1.6 1.6–1.8 1.0 ± 0.4 1.0 0.47 ± 0.09 1.5 ± 0.1 1.1 ± 0.1
Lu 32 950 0.4 ± 0.01 0.30–0.45 0.45–0.50 0.50–0.60 0.35 ± 0.02 0.35 0.29 ± 0.02 0.33 ± 0.05 0.40 ± 0.01
Nd 50 1300 33 ± 2 15–45 45–55 55–65 26 ± 2 29 12 ± 4.7 36 ± 3 25 ± 3
Sm 44 1270 5.4 ± 0.3 2.5–7.0 7.0–8.5 8.5–10 4.6 ± 0.3 4.5 2.5 ± 0.3 6.5 ± 0.4 4.5 ± 0.5
Tb 45 1160 0.75 ± 0.03 0.5–0.9 0.9–1.1 1.1–1.3 0.60 ± 0.03 0.66 0.28 ± 0.06 0.84 ± 0.05 0.60 ± 0.02
Pr 15 375 4.2 ± 0.5 2.5–6.0 6.0–8.0 8–10 4.3 ± 0.3 4.4 4.7 ± 1.6 4.3 ± 0.3 4.1 ± 0.5
Gd 25 400 4.7 ± 0.4 2.5–6.0 6.0–7.5 7.5–9.0 3.8 ± 0.4 4.3 2.7 1.4 ± 1.7 5.5 ± 0.5
Dy 15 340 3.0 ± 0.4 1–4 4–5 5–6 2.7 ± 0.2 2.9 1.2 ± 0.3 1.8 ± 0.3 3.9 ± 0.4
Er 15 375 1.9 ± 0.1 1–2 2–3 3–4 1.6 ± 0.1 1.8 1.0 ± 0.25 1.5 ± 0.2 2.0 ± 0.1
Ho 5 330 0.52 ± 0.09 0.2–0.6 0.6–0.7 0.7–0.8 0.38 ± 0.02 0.50 0.07 – 0.57 ± 0.04
Tm 14 33 0.40 ± 0.04 0.3–0.55 0.55–0.65 0.65–0.80 0.26 ± 0.02 0.35 0.20 – 0.30 ± 0.03
Ga 249 10400 16 ± 1 9–25 25–35 35–45 17 ± 1 17 13 ± 1 14 ± 1 20 ± 1
Ge 60 4630 2.4 ± 0.2 1.2–3.0 3.0–4.0 4.0–5.0 2.4 ± 0.1 2.5 1.2 ± 0.2 3.0 ± 0.3 2.8 ± 0.2

Cation- and anion-forming lithophiles with variable valency

Ti 466 17700 3000 ± 100 1500–4600 4600–6200 6200–7800 2700 ± 100 2800 1200 ± 100 2100 ± 200 3900 ± 100
Zr 251 13300 120 ± 5 60–190 190–260 260–330 120 ± 5 200 74 ± 6 120 ± 10 150 ± 10
Hf 49 1290 4.2 ± 0.2 2.5–6.0 6.0–7.5 7.5–9.0 3.5 ± 0.3 4.5 2.2 ± 1.6 2.9 ± 0.3 3.8 ± 0.5
Th 99 6310 7.0 ± 0.4 4–11 11–15 15–19 7.2 ± 0.4 7.8 3.9 ± 0.6 5.0 ± 0.6 7.4 ± 0.6
Sn 170 8040 3.9 ± 0.3 2–10 10–15 15–20 5.6 ± 0.3 5.7 5.0 ± 0.7 4.0 ± 0.4 6.6 ± 0.4
V 653 25200 205 ± 15 100–400 400–600 600–800 180 ± 10 180 99 ± 23 250 ± 30 200 ± 10
Nb 39 1800 11 ± 1 7–15 15–20 20–25 10 ± 0.7 15 2.9 ± 1.0 17 ± 2 12 ± 1
Ta 40 680 0.7 ± 0.04 0.5–1.0 1.0–1.3 1.3–1.6 0.66 ± 0.06 0.8 0.17 ± 0.14 0.55 ± 0.22 0.8 ± 0.1
Mo 495 18480 20 ± 1.5 6–60 60–100 100–140 20 ± 3 14 16 ± 7 29 ± 3 18 ± 3
W 36 1380 2.9 ± 1.0 0–15 15–25 25–35 7.8 ± 1.4 2.7 8.1 ± 1.2 21 ± 5 2.4 ± 1.9
U 240 8400 8.5 ± 0.8 4–25 25–40 40–55 13 ± 2 9.9 10 ± 1.9 13 ± 2 14 ± 3
Re 48 670 0.9 ± 0.3 0.2–3.5 3.5–6.0 6–9 0.4 ± 0.3 0.8 0.5 ± 0.5 1.0 ± 0.2 0.2 ± 0.1

Metals-thiophiles
B 196 9460 56 ± 3 30–120 120–165 165–220 71 ± 5 65 4.3 ± 8 87 ± 17 81 ± 6
P 364 14,900 1400⁎ ± 160 930–220 2200–3000 3000–3800 1800⁎ ± 100 1300⁎ 710 ± 70 1200 ± 100 1200 ± 100
F 47 1630 660 ± 70 400–1500 1500–2000 2000–3000 830 ± 70 760 640 ± 70 720 ± 130 780 ± 100
Cl 25 450 300 ± 100 100–1000 1000–2000 2000–3000 420 ± 90 380 340 ± 80 400 ± 190 470 ± 160
Br 23 1070 13 ± 3 2–30 30–50 50–70 9.8 ± 1.7 12 13 ± 3 12 ± 4.6 7.0 ± 4.3
I 12 310 1.6 ± 0.2 – – – 1.3 ± 0.2 1.3 0.8 ± 0.1 – 1.6 ± 0.2
Cu 580 25,740 70 ± 3 35–150 150–230 230–310 87 ± 9 140 55 ± 26 100 ± 16 100 ± 8
Ag 220 9000 1.0 ± 0.1 0.4–2.4 2.5–4.0 4.0–5.5 1.6 ± 0.2 1.7 1.7 ± 0.6 1.0 ± 0.3 1.8 ± 0.2
Au 148 9120 7.0 ± 1.0 3–20 20–35 35–50 7.6 ± 3.9 9.7 4.9 ± 2.1 8.5 ± 1.3 8.8 ± 7.7
Zn 489 18,540 130 ± 10 60–300 – 470–640 140 ± 20 160 140 ± 43 160 ± 30 140 ± 20
Cd 57 2260 5.0 ± 0.6 2–12 300–470 19–26 6.9 ± 1.4 6.2 8.3 ± 3.3 9.0 ± 3.3 5.3 ± 1.3
Hg 54 1420 0.27 ± 0.03 0.2–0.6 12–19 0.8–1.1 0.23 ± 0.03 0.32 0.29 ± 0.07 0.18 ± 0.03 0.22 ± 0.03
In 7 176 0.7 – 0.6–0.8 – 2.4 – 0.3 0.01 4.6 ± 3.2
Pb 436 20,520 21 ± 1 10–40 – 60–85 26 ± 1 25 26 ± 2 17 ± 2 29 ± 2
Bi 20 2740 1.1 ± 0.3 0–4 40–60 6–10 2.0 ± 0.5 1.8 2.5 ± 0.6 3.4 ± 0.7 1.1 ± 0.8

Non metals-thiophiles
As 130 4190 30 ± 3 10–80 80–130 130–180 30 ± 3 58 34 ± 6 30 ± 11 27 ± 3
Sb 82 1930 5.0 ± 0.5 2–11 11–17 17–23 5.6 ± 0.8 5.3 6.8 ± 0.8 8.8 ± 3.9 3.6 ± 0.4
Se 94 1650 8.7 ± 1.4 3–30 30–50 50–70 7.8 ± 1.0 9.3 8.0 ± 0.8 12 ± 2 6.6 ± 1.7
Te 7 110 2.0 ± 0.3 1.3–3.0 3–4 4–5 2.1 1.8 4.2 0.3 1.7

Fe-group elements
Cr 562 21,900 96 ± 3 50–160 160–220 220–280 81 ± 5 93 45 ± 6 86 ± 12 100 ± 7
Mn 534 19,600 400 ± 20 200–800 800–1200 1200–1600 440 ± 30 1100 500 ± 50 250 ± 30 470 ± 30
Co 517 21,000 19 ± 1 10–30 30–40 40–50 14 ± 1 18 11 ± 1.1 11 ± 1.5 17 ± 2
Ni 638 23160 70 ± 2 40–140 140–210 210–280 67 ± 4 67 41 ± 6 63 ± 7 84 ± 6

(N – number of primary samples, n – number of analyses).

Calculations by Marina P. Ketris, 1990.
⁎ The asterisk means that calculation was made with including 0.01 phosphate contribution, as: chert:carbonate:terrigenic (+tuff):phosphate = 0.20:0.29:0.50:0.01.
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Table 2 Table 2 (continued)

Subclarkes for the black shale lithologies, ppm Elements Carbonate shales, KCa Chert shales, KSi Terrigenous and
1 1
volcanic-sedimentary
Elements Carbonate shales, KCa
1 Chert shales, KSi
1 Terrigenous and
shales, KAl
1
volcanic-sedimentary
shales, KAl
1
m n Me ± σMe m n Me ± σMe m n Me ± σMe
m n Me ± σMe m n Me ± σMe m n Me ± σMe Elements-siderophiles
Co 11 3540 11 ± 1.1 12 5410 11 ± 1.5 15 12010 17 ± 2
Typical cation-forming lithophile elements
Ni 13 4290 41.6 12 5460 63 ± 7 15 13400 84 ± 6
Li 9 1580 24 ± 10 8 930 19 ± 2 13 2010 44 ± 2
Rb 11 1720 39 ± 4 11 1700 47 ± 6 14 1660 93 ± 9 Calculations by Marina P. Ketris, 1990.
Cs 5 1550 4.1 ± 0.8 5 490 3.0 ± 1.6 10 1140 5.9 ± 1.0 m - number of stratons, n - number of analyses, Me - straton median, σMe – standard
Tl 5 1440 0.7 ± 0.8 3 380 4.8 ± 2.1 6 890 2.6 ± 1.1 deviation of straton median.
Sr 11 2210 480 ± 40 12 4870 140 ± 20 15 8560 200 ± 10
Ba 12 2740 540 ± 90 12 4760 740 ± 70 15 7630 560 ± 60

Cation- and anion-forming elements with stable valency controlling factor. At any rate, it seems likely that they must not
Be 10 1420 1.6 ± 0.4 9 2490 2.2 ± 0.2 13 3900 2.4 ± 0.2 exceed the double-standard median limits:
Sc 10 1750 5.4 ± 0.3 11 1350 12 ± 2 14 3650 14 ± 1
Y 10 2230 12 ± 3.4 10 1530 25 ± 2 15 4860 29 ± 1 ðK1 ; K2 Þ b Me F 2δMe
La 10 1080 22 ± 3 9 710 31 ± 3 13 2350 31 ± 2
Ce 8 660 37 ± 12 8 340 41 ± 48 12 1740 61 ± 6 No doubt, all the preceding errors affect the final “true” estimation.
Pr 2 5 4.7 ± 1.6 2 29 4.3 ± 0.3 6 340 4.1 ± 0.5
Among them are:
Nd 4 260 12 ± 5 4 57 40 ± 10 9 780 25 ± 3
Sm 4 260 2.4 ± 0.3 4 200 5.0 ± 1.2 9 660 4.5 ± 0.5 - incorrectly defined original lithologies;
Eu 3 260 0.42 ± 03 3 41 1.3 ± 0.3 8 990 1.1 ± 0.06
Gd 1 4 2.7 3 27 1.4 ± 1.7 7 370 5.5 ± 0.5
- inaccurate weight coefficients, both lithologic (0.2:0.3:0.5) and
Tb 3 250 0.27 ± 0.03 4 66 0.72 ± 0.21 8 630 0.60 ± 0.02 stratigraphic (1:3);
Dy 2 2 1.2 ± 0.3 2 36 1.8 ± 0.3 6 340 3.9 ± 0.4 - number of lithological subclarkes different from each other;
Ho 1 1 0.07 4 330 0.57 ± 0.04 - number of Phanerozoic black shales different from pre-Phaner-
Er 2 5 1.0 ± 0.25 2 29 1.5 ± 0.2 6 340 2.0 ± 0. 1
ozoic ones.
Tm 1 1 0.2 3 32 0.30 ± 0.03
Yb 8 1790 1.8 ± 0.2 8 910 2.8 ± 0.3 13 2820 2.9 ± 0.2 For example, assumed weight coefficients for carbonate (0.3) and
Lu 3 260 0.28 ± 0.01 7 550 0.40 ± 0.01
terrigenous shales (0.5) may differ for Paleozoic platforms (more than
Ga 12 1880 13 ± 1 10 2640 14 ± 1 15 5880 20 ± 1
Ge 9 1820 1.2 ± 0.2 7 930 3.0 ± 0.3 10 1870 2.8 ± 0.2 0.3) and Mesozoan geosynclines (more than 0.5), respectively.
As follows from the above discussion, we are very well aware of all
Cation- and anion-forming elements with variable valency the inaccuracy of the Сlarke values we propose. It should be noted,
Ti 13 3750 1200 ± 100 11 4100 2100 ± 200 15 9810 3900 ±100 however, that they are no less accurate than the Clarke values for the
Zr 11 2690 74 ± 6 10 4470 140 ± 10 15 6040 150 ± 10
Hf 3 260 2.2 ± 2.8 3 41 3.1 ± 2.4 8 780 3.8 ± 0.5
Earth's crust and the ocean widely referred to in literature. From all
Th 8 1440 3.9 ± 0.6 8 1890 4.2 ± 0.7 14 2470 7.4 ± 0.6 the variety of strongly diverging values, Vinogradov (1962) simply
Sn 10 1930 5.0 ± 1.3 10 1660 4.0 ± 0.4 13 4480 6.6 ± 0.4 chose the figures he thought adequate. No doubt our Clarke values will
V 14 4790 99 ± 23 12 6550 250 ± 30 15 13870 200 ± 10 be revised in the not so distant future. Nevertheless, the Clarkes
Nb 6 1170 2.9 ± 1.0 7 1750 17 ± 2 11 1880 12 ± 1
proposed here are presently quite useful.
Ta 3 3 0.17 ± 0.12 3 41 0.55 ± 0.06 5 430 0.83 ± 0.09
Mo 13 3770 16 ± 7 12 6220 29 ± 3 15 8490 18 ± 3
W 4 690 8.1 ± 1.2 2 70 21 ± 5 10 530 2.4 ± 1.9 3. Estimation of trace elements Clarkes for coals
U 10 1230 10 ± 1.9 11 3480 13 ± 2 15 3700 14 ± 3
Re 4 440 0.5 ± 0.5 3 110 1.0 ± 0.2 4 120 0.2 ± 0.1 As was mentioned above, such calculations were made by several
Typical anion-forming lithophile elements
researchers, but there are many difficulties in the calculation.
B 9 1970 43 ± 8 10 2930 87 ± 17 14 4560 81 ± 6
P 13 2980 710 ± 70 12 3490 1200 ± 100 15 8200 1200 ± 100 3.1. Coal-basis and ash-basis Clarkes
F 9 820 640 ± 70 6 210 720 ± 130 13 600 780 ± 100
Cl 6 100 340 ± 80 2 58 400 9 290 470 ± 160
Up to 1970–1980, coal was mostly not directly analyzed for trace
Br 3 600 13 ± 3 2 11 12 ± 5 7 460 7.0 ± 4.3
I 4 39 0.77 ± 0.04 5 270 1.6 ± 0.2 elements but through an analysis of coal ash. Standard coal ashing was
performed at 750 °C (in USA and many West countries), or at 850 °C
Metals-sulfophiles (in former USSR and now in Russia)6. It is well known that some
Cu 14 5840 55 ± 26 11 6170 100 ± 16 15 13730 100 ± 8 elements may be almost fully (Hg, I, Br), or partly (Ge, Mo, etc.)
Ag 9 730 1.7 ± 0.6 12 3320 1.2 ± 0.2 14 4810 1.9 ± 0.3
Au, ppb 6 650 4.9 ± 2.1 5 2420 8.5 ± 1.3 10 6050 8.8 ± 7.7
volatilized by high-temperature ashing. Trace element loss may be
Zn 14 4130 140 ± 43 12 3390 160 ± 30 15 11030 140 ± 20 minimized by low-temperature ashing (~130–150 °C) by means of
Cd 5 680 8.3 ± 3.3 4 110 9.0 ± 3.3 8 1470 5.3 ± 1.3 radio-frequency exposure in oxygen plasma (Gluskoter, 1965). This
Hg 8 560 0.29 ± 0.07 5 400 0.18 ± 0.03 9 460 0.22 ± 0.03 excellent method, is, however, time-consuming and for this reason is
In 1 3 0.3 1 1 0.01 5 220 4.6 ± 3.2
not widely acceptable.
Pb 13 4580 26 ± 2 12 5670 17 ± 2 15 10280 29 ± 2
Bi 5 1140 2.5 ± 0.6 2 150 3.4 ± 0.7 8 1450 1.1 ± 0.8 So, up to end of 1980s, the content of trace element in coal (coal-
basis content) was obtained by recalculation from the content in ash
Nonmetals-sulfophiles (ash-basis content). Such recalculation may lead to underestimation of
As 9 840 34 ± 6 10 900 30 ± 11 14 2460 27 ± 3 coal-basis figures, and, as a result, to underestimation of coal-basis
Sb 7 610 6.8 ± 0.8 9 480 8.8 ± 3.9 12 840 3.6 ± 0.4
Se 9 370 8.0 ± 0.8 9 730 12 ± 2 11 550 6.0 ± 1.7
Clarkes.
Te 1 25 4.2 1 2 0.03 2 80 1.7 During the last decades of 20th century, several direct methods of
coal analysis were introduced in coal geochemistry, and first of all –
Elements-siderophiles INAA, instrumental neutron activation analysis. So, many directly
Cr 13 3820 45 ± 6 12 5090 86 ± 12 15 13040 100 ± 7
Mn 13 4540 500 ± 50 12 4970 250 ± 30 15 10100 470 ± 30
6
Nonstandard ashing (550 °C, with an air access) used in USSR and USA for special
(continued on next page)
intent – following analyses of ash for trace elements.
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142 M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148

obtained coal-basis figures appeared in the literature. Now a new

opportunity appears – to recalculate coal-basis figures to ash-basis
ones.
If the analysis of coal ash was earlier simply “a technical tool”
(because a direct analysis of coal was too hard and unreliable
procedure), have we any need for the “ash Clarkes” today? Yes, we
have such need: for the calculation of important geochemical values,
“coal affinity indexes” (or “coalphile coefficients), as we will discuss
below.

3.2. “Coal-affinity” (coalphile) indexes

Goldschmidt (1935) first calculated the “enrichment coefficients”

of coal ash by comparison of element content in coal ash and Earth's
crust Clarke value. For example: the Earth's crust-As Clarke value was
assumed to be 5 ppm, and As content in As-rich ashes was determined
as 500 ppm; so, enrichment coefficient was 500/5 = 100.
Later Yudovich (1978) used coal ash Clarke values (instead of
“enriched ashes”) and Clarkes of sedimentary rocks for such
calculation. These figures (enrichment coefficients) were named as
“typomorph coefficients”, and were widely cited in Russian and
Bulgarian literature7. More recently, this poor term was substituted
for coalphile coefficient (index), or coal affinity index (Yudovich and
Ketris, 2002).
What does a coal affinity index mean? – It shows, how efficiently coal
acted as a geochemical barrier for trace elements, during all its geologic
history. The more coal concentrated trace elements from environment
compared with sedimentary rocks, the greater would be the coal affinity
index. A researcher could compare coal affinity indexes for different
elements in given coal field, given coal basin, or province; for the coals of
different rank; and for the same coal field (basin, province) but for
different elements. For example, As coal affinity index is 50 ppm/
11 ppm= about 5 (Yudovich and Ketris, 2005a,d), and Hg coal affinity
index is 0.75 ppm /0.05 ppm = 15 (Yudovich and Ketris, 2005b,c,d). So,
Hg is threefold more coalphile element than As.

3.3. Calculation method

All calculation procedures may be divided into several stages

(Ketris and Yudovich, 2002):
1) analytical data collection; 2) preliminary data processing and
formation of basic tables; 3) using basic tables, formation of
sufficiently homogeneous statistical data samples (data assemblages),
and calculation of sample-averages; 4) using sample-averages,
plotting of frequency histograms and evaluation of the Clarke value,
as median.
Fig. 4. A sketch showing a procedure of stepped averaging (Tkachev and Yudovich, 1975,
p. 124). The steps (levels): a – initial, the analyses of coal specimens; b – coal beds; c –
3.3.1. Analytical data collection
coal fields; d – coal areas (basins, provinces), e – final totality of the areas (= global
This is very time-consuming and the hardest part of all the work. totality of statistical samples). 1 – anyone object of the given step (level); 2 – specific
We collected coal-analyses data nearly 45 years. From the literature, it object of this step (level), for which are shown its lower (composing) components.
is necessary to extract the following data: (a) coal locality (country,
basin, coal field (deposit), coal seam; (b) coal rank and geological age;
(c) ash yield on dry matter (Ad, %); (d) how units are used (%, ppm, mg/g
etc.), and basis – coal or ash; (e) number of coal specimens (analyses).
Unfortunately, only in few instances we could obtain all the 1972, 2003), and the use of such figures may sharply change the
information! Often, a part of information needed was lacking. For sample average. The other important question arises: was the given
example, if the coal locality was lacking, such analytical data have to be coal influenced secondary processes? Such data may also distort a
rejected. homogeneity of the statistical sample.
The stratigraphic data were needed in order to not include In literature prior to 1980, a simultaneous analysis presentation on
different-age coals within an united statistical sample. We need also an ash- and on a coal basis was rare; so, we needed to know an ash
to know: if the data collected belong to coal beds or coal inclusions? yield in order to obtain the lacking figure by recalculation. If an ash
The latter may be extremely enriched in trace elements (Yudovich, yield was lacking, we tried to evaluate it using all the available
information sources (reference books, special monographs, etc.).
In many Soviet papers (where in fact, many thousand spectro-
7
See numerous papers published by Greta Eskenazy, Jordan Kortensky, Stanislav graphic analyses were averaged), the number of analyses was lacking.
Vassilev, and some others. In such instances, we needed to get only some “conditional” number
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Fig. 5. An example of the “appropriate" plot: zirconium (Yudovich, Ketris, 2006a,b,c, p. 285). N – number of analyses, n – number of statistical samples, Me – the median of statistical
samples.

of analyses. This means that our “number of analyses” sometimes did 3.3.3. Stepped averaging and final median calculation
not contain enough accurate information (tends to be underestimated). After basic tables were formed, we could obtain the assemblage of
statistical samples (and their averages), which would be used for the
final Clarke calculation. Each statistical sample embraces the analyses
3.3.2. Preliminary data processing and formation of basic tables of a coal basin or large coal area (region). All the analyses included are
Preliminary data processing may start even during data collection: to be averaged. If the collected data allowed, we constructed two to
the individual figures (belonging to each coal specimen) being four statistical samples for big coal basins (provinces) – for example,
averaged – if such average is lacking in original text. As elemental for some industrial regions (within Donets basin, Ukraine), coal fields,
information units, we assumed a coal bed- or coal-field averages. For or other geographical units. The number of such “intra-basinal”
example, if there were several figures for one coal bed, we calculated statistical samples nearly corresponded with coal geological resources
the coal-bed average and put it in the basic table. If there were the of the given basin.
figures for three coal beds, these three figures were put in basic table, The full concept involves stepped (successive) averaging, from
etc. If the set of analyses had very sharp anomalies (for example, one minor to large: one coal bed ⇒ several coal beds ⇒ coal field (deposit)
to two order-of-magnitude more than coal geochemical background), ⇒ coal area (several coal fields) ⇒ coal basin or province ⇒ totality of
such figures, as a rule, were not included in average calculation. the coal basins (=assemblage of statistical samples), i.e. Clarke value
As a result, for each element we created two basic tables, for brown totality, comprising several dozen random (statistical) samples
and hard coal, as following: representing many thousands of analyses (Fig. 4).
Hard (brown) coals For example, coal Clarke value of As was calculated using totality,
consisting of 119 statistical samples (and about 21,000 analyses) – for
Country Coal basin Coal Geologic n Ad E, ppm E, ppm Reference hard coals, and 66 statistical samples (and about 21,000 analyses) – for
(province, field, age on coal on ash (source of brown coals (Yudovich and Ketris, 2005a). On the steps, the averages
region, area) bed basis basis data) were calculated as arithmetic mean (if the sample was more
homogeneous), or as median (if the sample was less homogeneous).
In such a table, n means the number of analyses, Ad – ash yield, %, E – Following our good experience in black shale geochemistry
a chemical element. (Yudovich and Ketris, 1994), we use a sample totality median (Me)
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144 M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148
as a Clarke value estimation. As an estimation of the median accuracy
(σMe) we use the value
pffiffiffiffiffi
σ Me = ðQ3 − Q1 Þ=2 n; ð16Þ
where Q1 and Q3 – two distribution quartiles, corresponding 1/4 and
3/4 of the cumulative frequency.
Although a Clarke value (a median) is estimated analytically, it is
very instructive to plot a frequency histogram. The distribution of
trace element contents in coal is, as a rule, log-normal; that is why, for
plotting the logarithmic scale is often used. The plot character could
suggest: how “good” is the totality studied. If the histogram is “right”
(for example – near to log-normal), the totality could be attested as a
“good” one (Fig. 5); in opposite case, we can think the totality is too
small and not representative of natural coals (Fig. 6). In such a case, we
need to get some new analyses for a better Clarke estimation. In fact,
the elements with “right” histograms nearly “do not react” upon new,
supplementary analyses – their Clarke value could only little vary (as a
rule – not more than within accuracy range of median, i.e. ±1σMe). On
the contrary, some rare, poorly studied elements (such as Au, Pd, Tl, In,
Te, Cl, I, and some others) may, in future, change their Clarkes more
appreciably.
The other (well known) histogram characteristic is its σMe value
compared with Me value. If these figures are comparable (very large
variance of the statistical distribution), the Clarke value is, of course,
Fig. 6. An example of the irregular plot: iodine.
not very reliable; if σMe bb Me, the opposite is true. For example,
average content of Pd in brown coal ashes was estimated only over
eight statistical samples (nearly 50 analyses) as 0.066 ± 0.027 ppm.
Such a figure appears to be too high and dubious, accounted for
Chinese Pd-rich coals contribution. There is no doubt, as the sample
assemblage is extended, the Pd Clarke in coal will be changed.
For the REE, one other criterion exists: the picture of the
standardized (normalized) curve. As example, Tm has some peak on
such curve, that distinguishes Tm from the neighboring REE. It may
mean that the Tm coal Clarke is now overestimated, and may be
amended in future, as more information would be available.
3.3.4. Calculation results
The results of the calculations are shown in Table 3 and 4.
The last column in Table 3 represents coal affinity indexes,
calculated using our coal Clarkes and modern weighed Clarkes for
sedimentary rocks, calculated by Grigoriev (2003) using the Ronov's
sedimentary shell model (Ronov, 1980; Ronov et al., 1990). It is of note,
the coal affinity indexes are calculated on the base of averaged ash
Clarkes, i.e. (element Clarke in hard coal ash + element Clarke in brown
coal ash)/2. For example, lithium: (49 ppm + 82 ppm)/2 ≈ 66 ppm;
66 ppm/33 ppm = 2 (coal affinity index).
It should be noted that some Clarkes in Table 3 are based on small
statistical samples or/and not very reliable analyses. Such (preliminary)
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Table 3
Coal Clarke values for trace elements

Elements Coals Coal ashes Clarke value of CAI

Brown Hard All Brown Hard All sedimentary rocks

Typical cation-forming lithophile elements

Li 10 ± 1.0 14 ± 19 12 49 ± 4 82 ± 5 66 33 2.0
Rb 10 ± 0.9 18 ± 1 14 48 ± 5 110 ± 10 79 94 0.84
Cs 0.98 ± 0.10 1.1 ± 0.12 1.0 5.2 ± 0.5 8.0 ± 0.5 6.6 7.7 0.86
Tl 0.68 ± 0.07 0.58 ± 0.04 0.63 5.1 ± 0.5 4.6 ± 0.4 4.9 0.89 5.5
Sr 120 ± 10 100 ± 7 110 740 ± 70 730 ± 50 740 270 2.7
Ba 150 ± 20 150 ± 10 150 900 ± 70 980 ± 60 940 410 2.3

Cation- and anion-forming elements with stable valency

Be 1.2 ± 0.1 2.0 ± 0.1 1.6 6.7 ± 0.5 12 ± 1 9.4 1.9 4.9
Sc 4.1 ± 0.2 3.7 ± 0.2 3.9 23 ± 1 24 ± 1 23 9.6 2.4
Y 8.6 ± 0.4 8.2 ± 0.5 8.4 44 ± 3 57 ± 2 51 29 1.8
La 10 ± 0.5 11 ± 1 11 61 ± 3 76 ± 3 69 32 2.2
Ce 22 ± 1 23 ± 1 23 120 ± 10 140 ± 10 130 52 2.5
Pr 3.5 ± 0.3 3.4 ± 0.2 3.5 13 ± 2 26 ± 3 20 6.8 2.9
Nd 11 ± 1 12 ± 1 12 58 ± 5 75 ± 4 67 24 2.8
Sm 1.9 ± 0.1 2.2 ± 0.1 2.0 11 ± 1 14 ± 1 13 5.5 2.4
Eu 0.50 ± 0.02 0.43 ± 0.02 0.47 2.3 ± 0.2 2.6 ± 0.1 2.5 0.94 2.7
Gd 2.6 ± 0.2 2.7 ± 0.2 2.7 16 ± 1 16 ± 1 16 4.0 4.0
Tb 0.32 ± 0.03 0.31 ± 0.02 0.32 2.0 ± 0.1 2.1 ± 0.1 2.1 0.69 3.0
Dy 2.0 ± 0.1 2.1 ± 0.1 2.1 12 ± 1 15 ± 1 14 3.6 3.9
Ho 0.50 ± 0.05 0.57 ± 0.04 0.54 3.1 ± 0.3 4.8 ± 0.2 4.0 0.92 4.3
Er 0.85 ± 0.08 1.00 ± 0.07 0.93 4.6 ± 0.2 6.4 ± 0.3 5.5 1.7 3.2
Tm 0.31 ± 0.02 0.30 ± 0.02 0.31 1.8 ± 0.3 2.2 ± 0.1 2.0 0.78 2.6
Yb 1.0 ± 0.05 1.0 ± 0.06 1.0 5.5 ± 0.2 6.9 ± 0.3 6.2 2.0 3.1
Lu 0.19 ± 0.02 0.20 ± 0.01 0.20 1.10 ± 0.10 1.3 ± 0.1 1.2 0.44 2.7
Ga 5.5 ± 0.3 6.0 ± 0.2 5.8 29 ± 1 36 ± 1 33 12 2.8
Ge 2.0 ± 0.1 2.4 ± 0.2 2.2 11 ± 1 18 ± 1 15 1.4 11

Cation- and anion-forming elements with stable valency

Ti 720 ± 40 890 ± 40 800 4000 ± 200 5300 ± 200 4650 3740 1.2
Zr 35 ± 2 36 ± 3 36 190 ± 10 230 ± 10 210 170 1.2
Hf 1.2 ± 0.1 1.2 ± 0.1 1.2 7.5 ± 0.4 9.0 ± 0.3 8.3 3.9 2.1
Th 3.3 ± 0.2 3.2 ± 0.1 3.3 19 ± 1 23 ± 1 21 7.7 2.7
Sn 0.79 ± 0.09 1.4 ± 0.1 1.1 4.7 ± 0.4 8.0 ± 0.4 6.4 2.9 2.2
V 22 ± 2 28 ± 1 25 140 ± 10 170 ± 10 155 91 1.7
Nb 3.3 ± 0.3 4.0 ± 0.4 3.7 18 ± 1 22 ± 1 20 7.6 2.6
Ta 0.26 ± 0.03 0.30 ± 0.02 0.28 1.4 ± 0.1 2.0 ± 0.1 1.7 1.0 1.7
Mo 2.2 ± 0.2 2.1 ± 0.1 2.2 15 ± 1 14 ± 1 14 1.5 9.3
W 1.2 ± 0.2 0.99 ± 0.11 1.1 6.0 ± 1.7 7.8 ± 0.6 6.9 2.0 3.5
U 2.9 ± 0.3 1.9 ± 0.1 2.4 16 ± 2 15 ± 1 16 3.4 4.7

Typical anion-forming lithophile elements

B 56 ± 3 47 ± 3 52 410 ± 30 260 ± 20 335 72 4.7
P 200 ± 30 250 ± 10 230 1200 ± 100 1500 ± 100 1350 670 2.0
F 90 ± 7 82 ± 6 88 630 ± 50 580 ± 20 605 470 1.3
Cl 120 ± 20 340 ± 40 180 770 ± 120 2100 ± 300 1440 2700⁎ 0.53
Br 4.4 ± 0.8 6.0 ± 0.8 5.2 32 ± 5 32 ± 9 32 44 0.73
I 2.3 ± 0.4 1.5 ± 0.3 1.9 13 ± 2 12.2 ± 5.4 12.6 1100 0.01

Metals-sulfophiles
Cu 15 ± 1 16 ± 1 16 74 ± 4 110 ± 5 92 31 3.0
Ag 0.090 ± 0.020 0.100 ± 0.016 0.095 0.59 ± 0.09 0.63 ± 0.10 0.61 0.12 5.1
Au, ppb 3.0 ± 0.6 4.4 ± 1.4 3.7 20 ± 5 24 ± 10 22 6.0 3.7
Zn 18 ± 1 28 ± 2 23 110 ± 10 170 ± 10 140 43 3.3
Cd 0.24 ± 0.04 0.20 ± 0.04 0.22 1.10 ± 0.17 1.20 ± 0.30 1.2 0.80 1.5
Hg 0.10 ± 0.01 0.10 ± 0.01 0.10 0.62 ± 0.06 0.87 ± 0.07 0.75 0.068 11
In 0.021 ± 0.002 0.040 ± 0.020 0.031 0.11 ± 0.01 0.21 ± 0.18 0.16 0.043 3.7
Pb 6.6 ± 0.4 9.0 ± 0.7 7.8 38 ± 2 55 ± 6 47 12 3.9
Bi 0.84 ± 0.09 1.1 ± 0.1 0.97 4.3 ± 0.8 7.5 ± 0.4 5.9 0.26 23

Nonmetals-sulfophiles
As 7.6 ± 1.3 9.0 ± 0.7 8.3 48 ± 7 46 ± 5 47 7.6 6.2
Sb 0.84 ± 0.09 1.00 ± 0.09 0.92 5.0 ± 0.4 7.5 ± 0.6 6.3 1.2 5.3
Se 1.0 ± 0.15 1.6 ± 0.1 1.3 7.6 ± 0.6 10.0 ± 0.7 8.8 0.27 33

Elements-siderophiles
Cr 15 ± 1 17 ± 1 16 82 ± 5 120 ± 5 100 58 1.7
Mn 100 ± 6 71 ± 5 86 550 ± 30 430 ± 30 490 830 0.59
Co 4.2 ± 0.3 6.0 ± 0.2 5.1 26 ± 1 37 ± 2 32 14 2.3
Ni 9.0 ± 0.9 17 ± 1 13 52 ± 5 100 ± 5 76 37 2.1
Pd 0.013 ± 0.006 0.001 ± 0.002 0.0074 0.066 ± 0.027 0.007 ± 0.011 0.037

(continued on next page)

(continued on next page)
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146 M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148
Table 3 (continued)
Elements Coals
Brown Hard All
Elements-siderophiles
Ir 0.002 ± 0.006 0.001 ± 0.0003 0.002
Pt 0.065 ± 0.018 0.005 ± 0.003 0.035
Calculations by Marina P. Ketris, 2005.
CAI – coal affinity indexes (“coalphile indexes”).
CAI = average element concentration in coal ash/Clarke value in sedimentary rocks.
⁎ Cl Clarke value in sedimentary rocks – according to (Ronov et al., 1990).
⁎⁎The brackets mean that calculated Clarke value (based on small statistical samples or not very reliable analyses) is of minor adequacy (reliability). Such values could be strong
changed in future.
9
The ± figures mean ±1σMe
Clarkes could be strong changed in future; corresponding figures are
shown in the brackets.
4. Discussion in coal geochemistry
The data in Table 3 allow us to make some comparisons and raise
issues.
4.1. The values from 1985 and 2005: a comparison.
Due to new analytical methods and the great information gain, the
2005 Clarke estimations for some elements were appreciably changed
compared with 1985 estimations. Among these elements:
Li, Rb, Ag, Ti, Nb, As, Cl – for all coals; Cu, Be, B, Sc, Th – for brown
coals; Hg – for hard coals.
Other Clarke estimates also changed but less, only within 20–40%:
Ga, Y, Yb, Р – for all the coals; Ba, B, Cd, Co – for brown coals; Zn, Sc, Mo,
Mn – for hard coals.
Finally, many Clarke values have kept within the calculation
accuracy range: Sr, Ge, Zr, Sn, V, F, Cr, Ni – for all the coals; Hg, Zn, Mo,
Mn – for brown coals; Rb, Be, В, Cu, Th – for hard coals.
4.2. Comparison of brown and hard coal Clarkes
Such a comparison allows analysis of coal rank influence on coal
geochemistry. Coal “metamorphism” is the thermal epigenetic
process, involving hot brines and fluids influencing coal beds. These
processes not only changed coal organic matter, but may greatly
change the trace element contents by means of their input or output
(Yudovich, 1978; Yudovich and Ketris, 2002). However, this (obvious)
issue is far from universal. It is known that, in general, hard coals are
Paleozoic, and brown coals are Mesozoic and Cenozoic. This means
that in some instances the geochemical difference “brown coals vs.
hard coals” may be primary, accounted for the large initial difference
of Paleozoic and Mesozoic-Cenozoic coal-forming flora.
As seen from Table 3, brown coals are enriched in B, U, and Mn. For
all three elements, one can suggest their output during thermal
metamorphism of the coal organic matter. More elements are
enriched in hard coals compared with brown ones. Weak enrichments
include Co, Ge, V, Pb, Se, and strong ones include Rb, Be, Zn and Ni.
Only for the evident sulfophile elements (such as Pb, Se, and Zn), such
enrichments could be caused by hydrothermal input related to coal
metamorphism. However, for litho- and siderophile elements (such as
Be, Cr, Co, Ni) such explanation appears to be dubious. It is not
excluded that primary coal-formed flora acted here as actual factor of
difference (Yudovich, 1978). Such (non-trivial) conclusion could
highlight some problems dealing with the biosphere evolution.
4.3. Coal affinity indexes
By analyzing ranges of the coalphile indexes (the last column in
Table 3), one can divide the elements in four groups:
(a) non-coalphile elements (coal affinity indexes are b1): I, Cl, Mn,
Br, Rb, Cs;
Coal ashes Clarke value of CAI
Brown Hard All sedimentary rocks
0.013 ± 0.031 0.007 ± 0.003 0.010
0.22 ± 0.04 0.038 ± 0.018 0.13
(b) weakly or moderate coalphile elements (coal affinity indexes
range from 1 to 2): Ti, Zr, F, Cd, V, Ta, Cr, Y, Li, P;
(c) coalphile elements (coal affinity indexes range from 2 to 5): Ni,
Hf, Sn, La, Co, Ba, Sc, Nb, Sr, Th, Ga, Cu, REE, Zn, W, Au, In, Pb, U, B,
Be;
(d) highly coalphile elements (coal affinity indexes N5): Ag, Sb, Tl, As,
Mo, Ge, Hg, Bi, Se.
The greater is the coal affinity index, the greater is the contribution
of an authigenic fraction of given trace element (represented by
organic or micro-mineral forms), and the less is one of a clastogenic
fraction (represented by macro-mineral forms (for example, silicatic).
Due to the new (weighed) Clarkes of sedimentary rocks (Grigoriev,
2003), some earlier estimations of coal affinity have drastic changed.
So, after the calculation of real evaporites contribution in sedimentary
shell (Ronov, 1980; Ronov et al., 1990), the weighted Clarkes of
halogens Cl, Br, and I in sedimentary rocks increased. This results in a
corresponding sharp decrease in their coal affinity indexes: halogens
“have transformed” from highly coalphile elements (Yudovich et al.,
1985; Yudovich and Ketris, 2006b) to non-coalphile ones8. Also, the
coalphile indexes of Au, Cd, Y, V, U, Cr have unexpectedly decreased,
and, in turn, indices of Tl, Zn, Hf, and In have unexpectedly increased.
The extreme coalphile indices of Bi and Se appear to be very
doubtful. Such strange figures could be accounted for errors in the
Clarke values for sedimentary rocks (and not for coal Clarkes errors?).
It is of note, these elements are often not analyzed; due to analytical
difficulties; see, for example, for Se (Yudovich and Ketris, 2006a). This
may be a factor.
5. Conclusion
Black shale Clarke values are the average trace element contents in
the World black shales. It is well known that black shales (carbonac-
eous, mainly marine sedimentary rocks) often are metalliferous and/
or bituminous: enriched in U, V, Mo, Re, many other trace elements,
and “shale oil”. That is why the Clarke values for black shale are very
important for each researcher dealing with oil- or ore-bearing black
shales. The tables of black shale Clarkes calculated by the authors in
1994 are presented here; these calculations are based on huge
information.
Coal Clarke values are the average trace element contents in the
World coals. The modern table of coal Clarkes is presented here,
calculated by the authors based on a very large amount of information
(thousands analyses of coal and coal ashes for trace elements).
The coal Clarkes are the scientific tool for many geochemical
comparisons and issues. First of all, coal Clarkes allow to compare
given (studied) coal with World geochemical background, and to
conclude: is the coal “normal” (near to the Clarke level), enriched or, in
8
However, J.C.Hower believes [personal communication, December 2008] that
halogens are coalphile on lithotype basis; vitrains have high Cl and Br where these
elements are high. But, Cl (or Br) are not universally high, so averaging takes in low-Cl
coals.
 Author's personal copy

M.P. Ketris, Y.E. Yudovich / International Journal of Coal Geology 78 (2009) 135–148 147

Table 4 efficiently coal acted as a geochemical barrier for trace elements

Number of analyses for coal Clarkes calculated during all its geologic history. A comparison of coalphile indexes with
Elements Brown coals (lignites) Hard (bituminous) coals each other allow to display a contribution of coal authigenic matter
n N n N (organics, sulfides etc.) in coal inorganics. On the other hand, the
Li 44 4914 84 11866 comparison of the coalphile indexes of the same element, but in
Rb 47 2898 79 12742 different coals, allow to see some non-obvious peculiarities of the coal
Cs 40 1808 70 11765 fields or coal basins. See, for example, numerous Bulgarian papers for
Tl 28 1588 49 6105 reference, such as on the coal geochemistry of In, W (Eskenazy, 1980,
Sr 78 16,335 113 27,052
Ba 76 16,108 127 18,433
1982); REE, Zr and Hf (Eskenazy, 1987a,b); Ta, Au (Eskenazy, 1990,
Be 80 48,001 118 114,256 1992); As and Sb (Eskenazy, 1995); Be (Eskenazy, 2006); B (Eskenazy
Sc 73 40,358 112 118,155 et al., 1994), Sr (Eskenazy and Mincheva, 1989), REE, U and Th
Y 72 59,505 106 117,643 (Kortenski and Bakardjiev, 1993); on coal inclusions with unique
La 57 44,689 105 22,232
contents of trace elements (Vassilev et al., 1995), etc.
Ce 44 4196 80 12,200
Pr 16 243 35 4871
Nd 30 1203 58 6828
Acknowledgements
Sm 35 1875 71 11,440
Eu 35 1913 73 11,578
Gd 18 453 42 5625 James Hower kindly and selflessly edited the original Russian-to-
Tb 34 1468 64 8640 English translation of this manuscript. Greta Eskenazy and Vladimir
Dy 26 989 49 5663 Seredin (the reviewers) made some valuable notes and corrections.
Ho 25 719 41 5298
Er 19 436 37 5272
We are very appreciative to Editor-in-Chief and our reviewers.
Tm 18 365 35 4792
Yb 61 31,120 94 95,812
Lu 32 1525 65 10,290 References
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