Reassessment of Polynov's Ion Mobility Series

ABSTRACT
Polynov (1937) calculated the relative mobilities of important elements in landscapes: CI > SO. > Ca > Na > Mg > K > Si > Fe >
Al. This series depicts a general weathering sequence that is essential to understanding many aspects of soil genesis and soil geography. It is
argued on theoretical grounds that Ca and Na are out of proper sequence in Polynov's series. Polynov estimated ion mobilities by comparing the average content of elements in igneous rock to the average content of the same elements in river waters. However, an estimated
80% of the rocks at the earth's surface, which supply most of the leachate to rivers, are sedimentary. Accordingly, Polynov's mobility
series was recalculated after adjusting rock chemical composition for the dominance of sedimentary rock types at the earth's surface. By
using the elemental composition of igneous rocks in his calculations, Polynov greatly overestimated the amount of Na relative to Ca in
rocks providing leachate to rivers. As a result, he significantly underestimated the mobility of Na relative to Ca. It is recommended that
Polynov's ion mobility series be modified to the following: Cl > S04 > Na > Ca > Mg > K > Si > Fe > Al. This study showed that Na
is much more mobile (relative mobility 18.0) than Ca (8.1), Mg (5.4), or K (3.5). Therefore, it is recommended that Na be placed in a
distinct mobility phase (lI) second in relative mobility to CI and S04 (1).

WEATHERED ROCK forms the raw material from which soils develop. Accordingly, scientists
studying soil genesis have long concerned themse1ves with the elements present in igneous rocks and
what happens to them in the weathering process. More than 90 chemical e1ements have been identified in
the crust of the earth, and they are organized into more than 1000 minerals. However, only eight elements
(02, Si, Al ,Fe, Ca, Na, K, and Mg) make up = 97 % by weight of crustal igneous rocks (Clarke, 1924;
Vinograov, 1962). Much of the physical and chemical aspects of soil genesis revolves around the fate of
these elements and the relationships among them .
Ions of just three elements - O2, Si, and Al - make up = 85 % of crustal rocks on a weight basis.
However, the 02- ion is so much larger than the other two that, on a volume basis; it virtually dominates
the crust. The ionic radius (R) of O2- is 0.13 um, compared with 0.04 um for Si4+'and 0.05 um for AlH.
This difference in radius does not appear so large. However, assuming that ions are spherical, their
volume is proportional to R3 The calculated volume (4/3nR3) of the 02- ion is 9.2 X 10-3 nnr'. The volume
of the Si4+ ion is 2.7 X 10-4 nm? or = 34 times smaller. The AI3+ on, with a volume of
5.2 X 10-4 nm", is = 18 times smaller than the 02- on. Considering these large differences in ion size, it
is not surprising that, on a volume basis, O2 makes up =94% of the earth'scrust. Goldschmidt (1954) has
. referred appropriately to the earth's crust as an oxysphere .

Crustal rocks can be viewed as a negatively charged O2 matrix in which small amounts of cations are
interspersed. For chemical rock weathering to occur, the positive1y charged ions such as Ca2+ and Na + must
be freed from the negatively charged matrix in which they are held. They then are either fiushed out of the
system by percolating water ar are recombined into new substances, such as soil clay. .

Polynov's Ion Mobility Series

Polynov (1937) estimated the relative ease with which different elements could be leached from rocks
and washed away in rivers. He did this by comparing the average composition of igneous rocks with the
chemical composition of the residue from river waters (Table 1).
Polynov's ion mobility series is Cl > S04 > Ca > Na > Mg > K> Si > Fe > Al. This series has been divided
into four mobility phases (Crompton, 1967): Phase I = Cl, 504; Phase II = Ca, Na, Mg, K; Phase rrr = Si02;
and Phase IV = Fe203 and Ah03. There are relatively small differences in mobility within each phase
compared with the differences between phases. For example, it should be possible for drainage waters to
remove a large portion of the ions in Phase I (Cl, S04) from weathering rock before significantly depleting
ions in the next phase (Na, Ca, K, Mg). Polynov argued that climate affects only the intensity of this process
not the sequence in which the elements are leached.
This ion mobility sequence and its underlying rationale have been widely accepted and used by soil
scientists as well as geochemists (Lutz and Chandler, 1966; Buol et al., 1980; Crompton, 1967; Fortescue,
1980). This simple and logical model is valuable in understanding many aspects of soil genesis under
different combinations of parent material chemistry and weathering intensity.
Furthermore, it is an excellent conceptual framework to use in explaining the processes of rock weathering
and soil formation to students. However, despite its wide acceptance and usefulness. There are compelling
reasons to ask if the sequence is exactly right, Specifically, Polynov listed Ca 2+ as .the most mobile of the
major cations . However, there are theoretical reasons (Huggins and Sun, 1946; Keller, 1968) to argue that

Na+ might be more mobile than Ca2+. Polynov based his series on a comparison of e1ements in river waters
with those in igneous rocks. However, Ronov and Yaroshevsky (1972) have recently estimated that 80% of
the rocks exposed at the earth's surface, those that provide the major leach- ate to rivers, are sedimentary.
Elemental analyses have shown (Clarke, 1924; Ronov and Yaroshevsky, 1972) that sedimentary and igneous
rocks differ profoundly in their chemical makeup. Therefore, it seemed probable that adjusting rock chemistry
for the dominance of sedimentary types at the earth's surface would significantly alter Polynov's relative
mobility series.
Table 1. Relative mobility of selected elements in landscapes (from
Polynov, 1937).

Element

Compositon
ofigneous
rocks

Compositon
of mineral
residue,
Tiver water

Relatve
mobility

Mobility
phase

% by wt.
el
SO,
ea

Na

Mg
K
SiO,
Fe,03
Al,03

0.05
0.15
3.60
2.97
2.11
2.57
59.09
7.29
15.35

6.75
11.60
14.70
9.50
4.90
4.40
12.80
0.40
0.90

100.00
57.00
3.00
2.40
1.30
1.25
0.20
0.04
0.02

I
I

II
II

II

II

III
IV
IV

Cation-Oxygen Bonds in Rocks

Huggins and Sun (1946) calculated the approximate energies of formation of cation-O": borids in
silicate glasses and minerals, assuming a reference state of gaseous ions (Table 2). As Keller (1968) has
stressed, the energies of formation calculated by Huggins and Sun(1946) are not quite the same as
changes in free energy. However, they accurately reflect the relative strength of different cation-O, bonds
in rocks. The greater the calculated energy - of formation, the stronger the bond between a given cation
and O2.- Theoretically, cations. whose oxides have higher energies of formation are less
susceptible to removal by weathering. The calculated energies of formation for oxides of AI andSi are very
large, indicating that these elements are bound very tightly in the O2 matrix, It is not surprising that both
rocks and soils consist of a rigid O-Si-Al framework in which the more basic (and more easily removed)
cations are dispersed,
Table 2 suggests that K + might be more mobile than either Ca 2 + or Na +. However, K + ions are
preferentially held by some silicate. minerals, which greatly reduces their mobility (Bohn et al., 1979).
Tabie 2 suggests that Na + ions would be leached from rocks more readily than Ca2+ ions. The bond
between Na and O2 is about one-third as strong as the bond _ between Ca and O2.
Therefore, under a given weathering regime, Na theoreti- cally.should be released from the rock structure'
more readily. Once released from the rock structure, ta is preferentially held (relative to Na) by the
exchange complex of clays in soils and sedimento Theoretically, one would expect a larger proportion of
Na than Ca to be lost to surface waters. Therefore, the ranking of Ca2+ as being more mobile than Na+ in
Polynov's series is counterintuitive.
Table 2. Energies of formation for oxides of common elements
in rocks (adapted from Keller, 1968).
Oxide
K2O
Na2O
CaO
MgO
Fe2O3
Al2O3
Sio4

gEnyoermfati
Kg cal mol
299
322
839
912
919
1793
3100

The overall objective of this study was to determine if reca1culating Polynov's ion mobility series
after adjusting for the dominance of sedimentary rock types at the earth's surface would significantly
affect the relative ranking of ion mobility. A specific objective was to determine if Na+ and Ca2+ are
out of sequence in Polynov's series.

PROCEDURES
Calculation of Rock Composition
The relative mobilities of the seven dominant cations in rocks were estimated using the same
approach as Polynov (1937). However, the elemental makeup of rocks was adjusted to account for the
dominance of sedimentary types near the earth's surface. The following rationale was used. Ronov and
Yaroshevsky (1972) estimated that sedimentary rocks occupy 80% of the earth's land surface.
Approximately 42 % of surface rock is shale or clay, 20 % is sandstone, and 18 % is carbonate.
Approximately 19% is volcanic in origin Clarke (1924), V'ino- gradov (1962), and others have
estimated the elemental makeup of different rock types. The weighted mean elemental content
of near-surface rocks was calculated (Table 3) as follows:

Ai = (O. 19I9n) + (0.42Sh) + (0.20Sa) + (O. 18Li) [1]

where Ai = weighted average percentage by weight of Element i in near-surface rocks, Ign = average
percentage by weight of Element i in igneous rocks, Sh = average percentage by weight of Elejnent i
in shale, Sa = average percentage by weight of Element i in sandstone, and Li = average percentage
by weight of Elemnt i in limestone.

Calculation of Relative Ion Mobility

Relative on 'mobility (RM) was calculated using elemental rock composition adjusted for nearsurface dominance of sedimentary types (Table 3), using the following formula:

RM = (RRlARC)/0.317

[2J

where RR = average composition of mineral residue of river water (percentage by weight) from Clarke
(1924), ARe = average elemental composition of near-surface rocks (percentage by weight) from Table 3, and 0.317 = (5.7/0.18)1100 (ratio of the residue of Cl in river waters to the
adjusted Cl content in rocks [Table 4]divided by 100) ..
Dividing by the factor 0.317 placed the mobility of elements on a relative scale, with Cl arbitrarily
assigned a mobility value of 100 (after Polynov; 1937). The values for relative ion mobility in Table 4 were
calculated in the same way as Polynov's values in Table 1. Therefore, the numbers are directly comparable.
Table 3. Elemental composition of near-surface rocks. t
Element
Cl
S04
Na
Ca
Mg
K
SiO,
Pe,O, + FeO
AI,O,

Igneous
(19%)

Shale
(42%)

0.05
0.12
2.84
3.66
2.09
2.59
59.12
4.50
15.34

0.21
. 0.54 '
0.96
2.23
1.46
2.69
58.11
6.47
15.40

Sandstone
(20%)
% by wt.
0.21'
0.54
0.33
3.96
0.70
1.10
78.31
1.38
4.76

Limestone
(18%)

Weighted
average

0.21
0.54
0.04
30.65
4.74
0.27
5.19
0.54
0.81

0.18
0.45
1.02
7.94
2.00
1.89
52.23
3.95
10.48

t Calculated frorn data of Clarke (1924), Clarke and Washington (1924),

Mason (1966), Jackson (1964), Ronov and Yaroshevsky (1972), and Vnogradov (1962).
.

.,

HUDSON: POLYNOV'S ION Me

Table 4. Relative mobility of elernents in landscapes. Rock composition adjusted for near-surface dominance of sedirnentary
types.

Elernent

Composition
of rocks

Composition
of minera!
residue,
river watert

Relative
mobility

Mobility
phase

% by wt.

CI
SO,
Na
Ca
Mg
K
SiO;
Fe,OJ
AhOJ

0.18
0.45
1.02
7.94
2.00
1.89
52.23
3.95
10.48

5.7
12.1
5.8
20.4
3.4
2.1
11.7
0.4
0.9

100.0
85.0
18.0
8.1
5.4
3.5
0.7
0.32
0.27

t Avg. of rivers of the world (Clarke, 1924).

RESULTS AND DISCUSSION

Rock Composition

I
II
li
li

m
IV
V
V

Adjusting elemental rock composition to account for the dominance of' near-surface rocks by
sedimentary types (Table 3) caused a relative decrease in all cations except Ca. Adjusting for Ca levels
in sedimentary rocks caused the overall estimate of Ca in surface rocks to more than double. The
estimated amount of Na was reduced by more than half. By weight, the ratio of Ca to Na in igneous
rocks is about 1.3:1.0. However, after adjusting for sedimentary losses and gains, the overall ratio. of
Cato Na in near-surface rocks is about 8: 1. Apparently, a lot of the original Na in igneous rocks was lost
in the process of weathering, translocation, and redeposition. In contrast, sedimentary processes
operating for long geologic periods have served to concentrate Ca in near-surface rocks.

Relative Mobility
Calculating relative mobility of elements after adjusting for near-surface rock composition resulted in
a significant change in the relative positions of Na and Ca (Table 4). ln Polynov's (1937) sequence, the
relative mobility of.Ca (3.00) is slightly greater than that of Na (2.40). That relationship was profoundly
reversed in this study. -The relative mobility of Na was 18.0, compared with 8.1 for Ca (Tble 4). The
relative mobility ranking of the other ions was unchanged. Based on these results, it is recommended
that Polynov's ion mobility sequence (CI > S04 > Ca > Na > Mg > K > Si > Fe > AI) be moditied to the
following: CI> S04 > Na > Ca> Mg > K > Si > Fe > AI. Considering the high mobility of Na
relative to the other basic cations, it is further recommended that tive mobility phases be recognized
(Table 4): Phase I = CI, S04; Phase II = Na; Phase III = Ca, Mg, K; Phase IV = Si02; and Phase V =
Fe20} and AhO}.
This study suggests that Polynov, by using the elemental composition of igneous rock in his calculations,
significantly overestimated the amount of Na in rocks providing leachate to rivers. At the same time, he grossly
underestimated the amount of Ca in near-surface rocks. As a result, the relative mobility of Na in landscapes
was greatly underestimated. The ion mobility series recommended here places Na in its proper position in the
mobility series. The ranking proposed here.is consistent with chemical theory and with empirical evidence concerning the amounts of Na retained in natural landscapes relative to Ca and other cations.
Proposing a change in Polynov's original ion mobility sequence is in no way meant to question the brilliance
of his pioneering work. In the 1930s, there was less appreciation than now for the sheer amount of sedimentary
debris on the earth's surface. This proposal, in simple terms, is merely the application of more complete
information
to clarify and. hopefully improve on Polynov's landmark achievement.
.