Journal of Inorganic Biochemistry 97 (2003) 1–7

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Hypothesis paper

A biogeochemical cycle for aluminium?

Christopher Exley*
Birchall Centre for Inorganic Chemistry and Materials Science, Keele University, Staffordshire ST5 5 BG, UK
Received 9 April 2003; received in revised form 27 June 2003; accepted 28 June 2003

Abstract

The elaboration of biogeochemical cycles for elements which are known to be essential for life has enabled a broad appreciation of the
homeostatic mechanisms which underlie element essentiality. In particular they can be used effectively to identify any part played by
human activities in element cycling and to predict how such activities might impact upon the lithospheric and biospheric availability of an
element in the future. The same criteria were the driving force behind the construction of a biogeochemical cycle for aluminium, a
non-essential element which is a known ecotoxicant and a suspected health risk in humans. The purpose of this exercise was to examine
the concept of a biogeochemical cycle for aluminium and not to review the biogeochemistry of this element. The cycle as presented is
rudimentary and qualitative though, even in this nascent form, it is informative and predictive and, for these reasons alone, it is deserving
of future quantification. A fully fledged biogeochemical cycle for aluminium should explain the biospheric abundance of this element and
whether we should expect its (continued) active involvement in biochemical evolution.
 2003 Elsevier Inc. All rights reserved.

Keywords: Biogeochemical cycle; Aluminium; Lithosphere; Biosphere; Abundance; Biochemical evolution; Essential elements; Toxicology

1. Introduction of an element relative to its abundance in the lithosphere

The most simple manifestation of a biogeochemical
cycle is an expression of the equilibrium that exists
between the abundance of an element in the lithosphere
(Earth’s crust) and the biosphere (biota).
Biogeochemical cycle
Lithospheric abundance ↔ Biospheric abundance
Lithospheric abundance of an element is a close approxi-
mation of its essentiality to living organisms in that all
elements essential to life are present in the lithosphere at
approximately 1 mM or above (data derived from [1]).
However, lithospheric abundance may be grossly mislead-
ing as an indicator of biological essentiality (aluminium
and silicon are prime exceptions being present at 3.0 and
10.0 M, respectively!) and it may be more informative to
look at the ratio of biospheric to lithospheric abundance
(B / L ratio) of an element (Table 1). (The obvious
exceptions of cadmium and to a lesser extent lead are
probably due to their extremely low lithospheric abun-
dance.) Indeed this expression of the biospheric abundance
*Corresponding author. Tel.: 144-1782-534-080; fax: 144-1782-712-
378.
E-mail address: c.exley@chem.keele.ac.uk (C. Exley).
(hereafter referred to as ‘relative abundance’) could be
loosely indicative of its natural selection through geobioch-
emical time and it may also be a more accurate reflection
of the mechanisms which dominate the biogeochemical
cycling of the element.
An excellent example of the latter consideration is the
relative abundance of the biologically essential element,
nitrogen. Its lithospheric abundance at approximately 2
mM is a poor indicator of its biological essentiality
whereas its B / L (it has the highest relative abundance in
humans though this drops to third highest for all biota) not
only demonstrates its biological significance but also the
extent to which its biogeochemical cycle is dominated by
its biotic cycle. This property of an element of being
effectively retained within its biotic cycle, or at least of
being rapidly returned to its biotic cycle, is inherent within
many of the elements which are essential to living things.
Obvious exceptions to this are metals. Dominated by ionic
chemistry and their propensity to form salts it is their
lithospheric abundance, as opposed to the ease with which
they are retained by their biotic cycles, which underlies
their biological essentiality.
It is noteworthy that the rankings for B / L and biotic
abundance are significantly different from each other and it
might be speculated that the order of the elements indi-

0162-0134 / 03 / $ – see front matter  2003 Elsevier Inc. All rights reserved.
doi:10.1016 / S0162-0134(03)00274-5
2 C. Exley / Journal of Inorganic Biochemistry 97 (2003) 1–7

Table 1
The abundance of elements in the lithosphere and in humans (expressed as ppm) and their relative abundance in humans
Rank Lithosphere (L) Humans (B) Humans / Lithosphere (B / L)
1 Oxygen 474 000 Oxygen 614 285 Nitrogen 1029
2 Silicon 277 000 Carbon 228 571 Carbon 476
3 Aluminium 82 000 Hydrogen 100 000 Hydrogen 66
4 Iron 41 000 Nitrogen 25 714 Phosphorus 11
5 Calcium 41 000 Calcium 14 286 Sulphur 8
6 Sodium 23 000 Phosphorus 11 143 Cadmium 7
7 Magnesium 23 000 Sulphur 2000 Oxygen 1.3
8 Potassium 21 000 Potassium 2000 Zinc 0.44
9 Hydrogen 1520 Sodium 1429 Calcium 0.35
10 Phosphorus 1000 Magnesium 271 Lead 0.121
11 Manganese 950 Iron 60 Potassium 0.095
12 Carbon 480 Zinc 33 Sodium 0.062
13 Sulphur 260 Lead 1.7 Copper 0.020
14 Nickel 80 Copper 1.0 Magnesium 0.012
15 Zinc 75 Silicon 1.0 Iron 0.0015
16 Copper 50 Aluminium 0.9 Nickel 0.00025
17 Nitrogen 25 Cadmium 0.7 Manganese 0.00021
18 Lead 14 Manganese 0.2 Aluminium 0.000011
19 Cadmium 0.11 Nickel 0.02 Silicon 0.000004
Data taken from [1].

cated by B / L has something to do with their biological
selection through geobiochemical time. Thus, if time’s
arrow is drawn from the highest to the lowest ranking then
B / L predicts that the geobiochemistry of the early Earth
would be dominated by covalent interactions stabilised by
anoxic, reducing environments and that the later advent of
more oxidising and less acidic conditions enabled the
selection of much of the bioinorganic chemistry, and metal
chemistry in particular, that is characteristic of life on
Earth today. This, admittedly tentative, suggestion places
aluminium not only at the bottom of the B / L rankings but
it also identifies aluminium as the last of the abundant
elements of the lithosphere to participate in the evolution-
ary processes which underlie life on Earth. Of course
silicon is also at the bottom of the B / L rankings for
humans though, through its association with diatoms and
other silica-forming organisms, it is likely to be higher
placed for all biota. Contrary to aluminium, there is also
substantial evidence that high concentrations of silicon in a
biologically available form, silicic acid, were present at an
early stage in the evolution of life on Earth [2] and so the
lack of known silicon biochemistry (as exemplified by the
absence of any known Si–C or Si–O–C linkages) in life
today [3] must either be a reflection of it being selected out
of biological chemistry or it is simply evidence of the
extremely limited chemistry of silicic acid [4].
Answers to difficult questions concerning the natural
selection of the elements during biochemical evolution
may be accessible through the study of elemental
biogeochemical cycles. Indeed such cycles may also
surrender predictions as to the future biological role of
such elements. So what is a biogeochemical cycle for
aluminium and what can be understood from constructing
such a cycle about the past, present and future of this
element.
2. Construction of a cycle
The idea behind the cycle was to try to encapsulate
within a single structure all of the major events which
together would determine the movement of aluminium
between the lithosphere and the biosphere (Fig. 1). Putting
this another way, I have tried to relate all of the processes
which, when acting as if they were a single event, would
explain the observed lithospheric and biospheric abun-
dances of aluminium (Table 1). Each of these ‘processes’
is represented as a cycle (for example, inorganic weather-
ing) carrying an elemental flux which will both influence
and be influenced by other related cycles. These exchanges
of aluminium are indicated as overlapping individual
cycles. For simplicity, cycles with significant interdepen-
dence are clustered (for example, primary mineral phases)
and the flux of aluminium between these clusters is shown
using black arrows (one way or reversible) in white circles.
Clusters are then organised into major cycles (for example,
lithospheric cycle) and fluxes of aluminium between these
are indicated with white arrows (one way or reversible) in
black circles. The major cycles are shown on a blue
background to suggest that the majority of the movement
of aluminium both within and between clusters of cycles
will take place in water. Neither the individual cycles, the
clusters of cycles nor the major cycles are drawn to scale.
However, the sizes depicted do offer some qualitative
suggestions about the relative amounts of aluminium that
 C. Exley / Journal of Inorganic Biochemistry 97 (2003) 1–7
are in flux in any one individual cycle, cluster of cycles or
major cycle.
3. The lithospheric cycle
In the lithospheric cycle aluminium in the form of
primary and secondary minerals and colloidal phases is
returned to the Earth’s crust via sedimentary processes
(Fig. 1). The retention of aluminium is extremely efficient
with 99.999% of cycled aluminium remaining within the
lithosphere. This efficiency is remarkable in that it is
achieved in spite of the fact that aluminium must be cycled
through a series of dissolution / precipitation events which
involve a significant proportion of cycled aluminium being
fully dissolved in the aqueous phase. Actually, the re-
tention of aluminium in the lithospheric cycle is ener-
getically favoured as the concentration of dissolved alu-
minium is limited by mineral phases of decreasing solu-
bility and hence lower free energy. These changes in the
relative free energy of the different cycled phases are
described in their simplest form in Fig. 2. Primary alu-
minium-rich minerals, such as feldspars, formed as magma
is cooled upon its incorporation into the Earth’s crust, are
dissolved from their parent rocks by weathering. Further
dissolution, primarily through carbonic acid weathering
[5], results in the formation of clay-like materials such as
kaolinite and other secondary mineral phases of increasing-
ly low solubility including hydroxyaluminosilicates and
aluminium hydroxide. These highly insoluble particulate
phases along with aluminium adsorbed on both mineral
and organic surfaces are eventually returned to the
emergent Earth’s crust through sedimentation and subduc-
tion into the magma. It is at this stage that aluminium
re-emerges as energetically unstable primary minerals and
the cycle is completed.
The role played by clays in limiting the solubility of
aluminium has been known for some time [6] whilst the
importance of hydroxyaluminosilicates has only recently
come to the fore [7,8]. Hydroxyaluminosilicates are
formed, for example in soil waters, by the reaction of
silicic acid with an aluminium hydroxide template [9].
They limit the solubility of aluminium by converting
amorphous aluminium hydroxide into a significantly more
insoluble and, importantly, kinetically inert phase [4].
Their formation is quite literally a geochemical brake on
an aluminium juggernaut which would otherwise career
into the biotic cycle.
The Achilles heel in the lithospheric cycle of aluminium
was in fact the advent of life on Earth! It was the arrival of
organic chemistry which added a new dimension to
mineral weathering [10] and the geochemical (now
biogeochemical) cycling of aluminium. The success of
inorganic phases such as hydroxyaluminosilicates in limit-
ing the solubility of aluminium is gained through the
kinetic inertia of their precipitates. They are formed rapidly
3
whilst their dissolution is extremely slow. However, the
precursors to these insoluble phases, for example the
putative Al(OH) 3(aq) , may not form in the presence of
competitive functional groups associated with organic
molecules. Under these conditions aluminium will form
soluble complexes with organic molecules, such as for
example humic acids in soil solution, which while posses-
sing high thermodynamic stability are kinetically more
labile. Soluble aluminium, either as free inorganic com-
plexes, such as Al 31 21
(aq ) or AlF (aq) , or chelates such as with
citric or humic acids, is the most efficient route of entry of
aluminium into biota and if the soluble aluminium com-
plex is small, uncharged and lipophilic (membrane perme-
able) then entry will be expedited [11].
4. The biotic cycle
In spite of its low relative abundance aluminium is
ubiquitous in the biosphere being found in all forms of life
on Earth. In the biotic cycle life forms are represented as
cycles for micro-organisms, plants, invertebrates, verte-
brates and humans with the relative size of the individual
cycles being a rough approximation of the proportion of
the total biotic abundance of aluminium in that cycle (Fig.
1). All of the cycles overlap with each other to show that
aluminium is cycled throughout the food chain.
The biospheric abundance of aluminium is not a reliable
estimate of its essentiality in living things (Table 1). For
example, in humans the body burden of aluminium is
considerably higher than for either manganese or nickel
and it is similar to copper. One might assume from such
data that aluminium like manganese, copper and to a more
limited extent, nickel, was an essential metal or one might
speculate that the higher than expected burden of alu-
minium reflected a bioinorganic chemistry which sup-
ported its systemic retention. There is no evidence to
support an essential function for aluminium in humans and
there is only limited information to suggest any essential
role in any other form of life. There is evidence in humans
[12], in animals [13] and in plants [14] of the lifetime
accumulation of aluminium though not necessarily by
design. The active (or by design) accumulation of alu-
minium would require its recognition by a biological
process in order that it and not just any other metal was
sequestered and retained. Whilst there is a burgeoning
body of evidence documenting a variety of responses of
organisms to environmental aluminium, for example,
apparent genetic resistance to aluminium in rice [15], I am
not aware of any instance where such a response has been
shown to be specific to this element. It is my understanding
that aluminium is more or less a silent visitor in biota. It
piggy-backs unrecognised on systems and processes which
have evolved to deal with either essential elements or
elements which, through natural selection, are already
excluded from biology. Biota neither recognise aluminium
4 C. Exley / Journal of Inorganic Biochemistry 97 (2003) 1–7

Fig. 1. A proposed biogeochemical cycle of aluminium. (Please see Section 2 for an explanation of its different components.).

as essential nor as toxic though evolutionary pressures
historically (if this can be used to express geobiochemical
time!) have their origins in the latter and if aluminium is
destined to evolve biological essentiality then we should
first expect a period of toxicity though only if a significant
biotic burden of aluminium can be sustained. The lack of
any known biological essentiality of aluminium should be
interpreted as a testimony to the efficiency with which the
lithospheric cycle has successfully excluded aluminium
from the biotic cycle. So why is the biospheric abundance
of aluminium still high relative to a number of essential
metals?
 C. Exley / Journal of Inorganic Biochemistry 97 (2003) 1–7
Fig. 2. The changes in relative free energy of the different phases of aluminium in the lithosphere. HAS, hydroxyaluminosilicates.
5. Integral biogeochemical cycles
Biogeochemical cycles representing either essential or
non-essential elements are always heavily influenced by
other biogeochemical cycles [16]. Integral to the biogeoch-
emical cycle of aluminium are those of silicon and
phosphorus (Fig. 1) [3,17]. Both are involved in the
mineral cycling of aluminium though the contribution of
aluminium phosphate minerals is dwarfed by that of the
aluminosilicates. Both also make significant indirect con-
tributions to the cycling of aluminium in the lithosphere,
for example, phosphates are significant sinks for
sedimented aluminium [18,19] and the association of
aluminium with silica frustules of diatoms, both occluded
and surface-adsorbed [20,21], is a key component of the
sedimentation of aluminium. The biogeochemical cycles of
silicon and phosphorus work in tandem to keep aluminium
out of the biosphere but how does the biogeochemical
cycle of aluminium impact upon the biospheric abundance
of phosphorus?
Recently we were able to demonstrate a novel mecha-
nism of silicon essentiality in biota which could well have
far reaching implications for the biogeochemical cycling of
each of these elements [22]. We were able to show in a
silicon-requiring organism (the diatom, Navicula pellicul-
osa) and a non-silicon requiring organism (the green alga,
Chlorella vulgaris) that silicon was essential in that in both
it increased the biological availability of inorganic phos-
phate in the presence of aluminium. Aluminium prevented
the growth of both of these organisms by limiting the
biological availability of phosphate. This aluminium-in-
duced limitation could be completely abolished by supple-
menting growth media with silicic acid. Phosphorus has a
high relative abundance in the biosphere (B / L ranking of
5
4) (Table 1) and this reflects its essentiality, not least in
energy storage and utilisation in aerobes, in biota. When
one takes into account the ease with which phosphorus
might be lost from its biospheric cycle by the precipitation
of inorganic phosphate [23] it is intriguing to speculate that
the evolution of its biological essentiality was entirely
dependent upon the biogeochemical cycle of aluminium
and in particular, the reaction of aluminium with silicic
acid to form hydroxyaluminosilicates.
6. A cycle of human intervention?
Whilst the relative abundance of aluminium in the
biosphere is extremely low (B / L rank is probably the
lowest for elements for which figures are available) (Table
1) it is still present in humans at levels similar to essential
metals such as copper. All estimates of the abundance of
aluminium in organisms including humans are modern
estimates. As such it is impossible to be sure if the
biospheric abundance measured today is a reflection of the
success with which aluminium is retained in the lithos-
phere or is an indication of an increased biospheric
abundance of aluminium due to the activities of humans. I
shall argue the latter by identifying a number of changes
within the biogeochemical cycle of aluminium which are
already in progress and make a burgeoning biospheric
burden of aluminium inevitable.
A significant change in the biogeochemical cycling of
aluminium has resulted from the man-made acidification of
the environment. This has occurred both through the
pollution of the atmosphere by gaseous acids, resulting in a
switch in the major acidifying anion of rainwater from
bicarbonate to sulphates and nitrates, and by the wide-
6 C. Exley / Journal of Inorganic Biochemistry 97 (2003) 1–7
spread application of intensive farming which is depleting
the buffering capacity of vast areas of the World’s agricul-
tural land. The acidification of rainwater has already
altered patterns of weathering in the lithosphere. We have
seen how subsequent stages in the weathering cycle
actually process aluminium through increasingly insoluble
mineral phases (Fig. 2). However, the success of this cycle
is dependent upon the release of silicic acid and a soil
solution pH which will support the reaction of this silicic
acid with aluminium to form hydroxyaluminosilicates [7].
When for example, carbonic acid weathering of feldspar is
replaced by sulphuric acid weathering the availability of
silicic acid is reduced by half and the pH of the edaphic
environment falls below 5.0 [24].
Carbonic acid weathering:
2KAlSi 3 O 8 1 2CO 2 1 11H 2 O
Feldspar
→Al 2 Si 2 O 5 (OH) 4 1 2K 1 1 2HCO 32 1 4Si(OH) 4
Kaolinite
This is an extremely slow reaction (10 215.5 mmol m 22
s 21 ) in which the dissolution of two moles of feldspar
mineral results in the release of four moles of silicic acid
and an environmental pH which will be determined by the
pKa of the bicarbonate anion, approximately pH 5.50.
Sulphuric acid weathering:
2KAlSi 3 O 8 1 H 2 SO 4 1 4H 2 O
Feldspar
→Al 2 Si 4 O 10 (OH) 2 1 2K 1 SO 4 1 2Si(OH) 4
1 22
Montmorillonite
This is a faster reaction (10 214.6 mmol m 22 s 21 ) and the
dissolution of two moles of feldspar mineral results in the
release of only two moles of silicic acid. The environmen-
tal pH will no longer be controlled by the weakly acidic
bicarbonate anion and so the acidity will be increased as
bicarbonate buffering is replaced by a more acidic system.
Whilst these stoichiometric equations are, admittedly, an
over-simplification of primary mineral weathering in a
natural system what they describe will be indicative of
how environmental acidification, such as occurs in regions
impacted by acid rain, will alter the biogeochemical
cycling of aluminium. For example, the enhanced deple-
tion of environmental silicic acid and concomitant
burgeoning edaphic acidity will ensure that aluminium
solubility control switches from the kinetically inert hy-
droxyaluminosilicates to kinetically much more labile
solubility controls such as amorphous aluminium hydrox-
ide and organoaluminium complexes. The increased labili-
ty of aluminium will be exacerbated by a subsequent
aluminium-induced limitation of biologically available
phosphate such that the significant environmental buffering
generated through, for example, algal growth and high
rates of photosynthesis, will also be rapidly depleted. We
have already seen that the key which opens the door for
aluminium to gain access to the biosphere is the increased
lability which comes with its increased solubility. Thus the
man-made acidification of the environment has resulted in
our increased exposure to aluminium particularly through
our diet much of the content of which either grazes or
grows on soils undergoing a progressive acidification.
Of course this unnoticed environmentally disguised
increase in our exposure to aluminium may not be as
significant as our exposure through our everyday use of the
metal. Whilst aluminium salts such as alum shales (potas-
sium aluminium sulphate, commonly referred to as potash)
have been mined, processed and used for many centuries
(was it aluminium used in drinking water purification and
not lead which really brought down the Roman empire?)
our (relatively) newly found ability to extract aluminium
from its ores has resulted in an unimaginably large
increase in our use of aluminium during the past 100 years
[25]. We are truly living in The Aluminium Age [12]. No
other metal is better suited for the myriad of different
applications of aluminium. Many of these applications
bring us into direct contact with the metal either in our
food and drink, through our cosmetics and prophylactics or
indeed in the air that we breath. All of life on Earth will be
experiencing an increased exposure to aluminium through
the man-made acidification of the environment. However,
humans are receiving a disproportionately large increase
through living in The Aluminium Age.
7. Conclusions
Biogeochemical cycles provide insight into the natural
selection and evolution of elements. The biogeochemical
cycle of aluminium provides a strong basis for the argu-
ment that aluminium has largely been excluded from
biochemical evolution by its efficient cycling within the
lithosphere. The activities of humans are influencing the
lithospheric cycling of aluminium such that the biospheric
burden of aluminium is burgeoning and, in addition, these
activities are circumventing this cycle to allow a much
more rapid flux of the metal into the biosphere and in
particular into humans. The consequences for life on Earth,
and ultimately humankind, of aluminium participating
actively in biochemical evolution are unknown. They may,
of course, already be unravelling in humans in the form of
chronic diseases such as Alzheimer’s disease [12] or
diabetes [26].
Acknowledgements
Dr. O. Exley is thanked for helpful discussions and for
preparing the figures.
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