Chapter 1.

THE CHEMICAL MOBILITY AND TRANSPORT OF ELEMENTS

IN THE WEATHERING ENVIRONMENT

M.R. THORNBER

INTRODUCTION

The aqueous solution, transport and precipitation of elements is of central

importance to weathering and geochemical dispersion. The hydrolysis and redox
reactions discussed in Chapter 1.2 are principally those that affect the msgor
elements, being responsible for the destruction of the primary rock-forming
minerals and the formation of the secondary minerals of the regolith. Of particu-
lar importance to geochemical exploration, however, are those reactions that
affect the generally less abundant elements associated with mineralization. These
are the reactions that are ultimately responsible for the nature of the surface
expression of mineralization in the regolith, particularly its size, intensity and
location. Geochemical anomalies formed as the result of chemical reactions and
transport involving water are referred to as hydromorphic and the process as
hydromorphic dispersion. The purpose of this chapter is to describe the
chemical principles involved in hydromorphic dispersion and the manner in
which individual elements or groups of elements behave in different weathering
environments.
The extent to which particular elements are mobilized by groundwaters during
weathering depends upon:
(1) the controls of solubility in aqueous solutions having various amounts of
other dissolved species (cations, anions and organic materials), and
(2) the interaction between these solutions and the complex surfaces of
primary and secondary minerals. Interactions between the two phases take place
at every point on the interface, which is depicted in a schematic cross section
shown in Fig. 1.5-1.
The various elements may be:
(a) held within the mineral crystal lattice;
(b) loosely bound within a layer of the changing potential field at the interface;
or
(c) mobile in solution, either solvated by the water molecules or "complexed"
with one or more other soluble ions. Mobility is also possible as colloidal
particles; these particles will have a similar dynamic interface with the solution
as depicted in Fig. 1.5-1.
80

Potenti

Surface potential

Helmholtz potential

Bulk solution
gp^O
potential

Solid Helmholtz
surface plane

Fig. 1.5-1. A schematic representation of a cross section through a solid/solution interface showing
the electrical potential change. Modified from Segall et al. (1982)

During dissolution, elements move from the crystal surface through the
charged layers into solution. For precipitation, the reverse is true. If other
elements are adsorbed at the interface these processes tend to be hindered and,
in the case of precipitation, may result in that element being coprecipitated or
bound into the crystal of the precipitate. The system is thus dynamic, involving
many kinetic phenomena; accordingly, the application of thermodynamic data,
such as solubility product constants, which are concerned with systems in
equilibrium, is not sufficient to give a full description of the likely chemical
mobility of an element. Nevertheless, as an initial consideration, solubility is
most important.
The aim of this chapter is to outline the major factors controlling the mobility
of the chemical elements in aqueous solutions at normal weathering tempera-
tures and to group the elements on the basis of similar behaviour. The groupings
presented are recognizably derived from the Periodic Table of the elements. The
classic books of Pourbaix (1963) and Baes and Mesmer (1976), and the recent
compilation of Eh-pH stability field diagrams by Brookins (1988) together give
an excellent basis for understanding the solubility of most elements where only
water is involved. Data concerning the complexing of elements by other ions has
been compiled by Sillen and Martell (1964; 1971) and Smith and Martell (1976).
Langmuir (1979) has given a very useful summary of this classical approach as it
relates to geochemical behaviour.
 81

SOLUBILITY

An element may be in solution as a cation, an anion or a neutral species,

depending upon the oxidation state it has been forced to adopt by the conditions
of the groundwater environment. As elements become more oxidized by losing
electrons, they become smaller in size and more positively charged. The solution
chemistry of an element is affected profoundly by changes in oxidation state; for
example, the lower + 2 oxidation state of the Fe11 ion is far more soluble than the
smaller-sized, higher + 3 oxidation state of Fe m (Fig. 1.5-2). In Fig. 1.5-2, the
stippled area shows the range of pH and oxidation potential, Eh, that can be
expected in groundwater environments. The range covers the conditions under
which Fe solubility is strongly controlled by both Eh and pH; the other ions in
solution are also affected due to co-precipitation with Fe oxides and by sec-

PH
Fig. 1.5-2. Solubility contours of Fe 2 + and Fe 3 + as a function of Eh and pH. The values on the
contours are the - log[total Fe] where [total Fe] is the total activity of iron in solution in moles/litre.
The stippled area represents the Eh and pH range that can be expected in natural weathering
environments.
82

OXYANIONS

Tc
Re

+2 +3
Oxidation state

Fig. 1.5-3. A plot of ionic radius, for six coordination, of the chemical elements as a function of the
oxidation state possible in natural weathering conditions. Derived from Shannon (1976), and
Hume-Rothery and Raynor (1958)

ondary Eh/pH control. A comparison of the six-coordinated ionic radii of all

elements with their particular oxidation states that can occur within the range of
Eh and pH expected during weathering is shown in Fig. 1.5-3.
 83

The elements can be divided into five groups, depending on the major factor
controlling their solubility. These groups, listed in Tables 1.5-1-1.5-5, are:
(1) anions,
(2) cations,
(3) insoluble oxides,
(4) variable oxidation state,
(5) metals.
The groups are not mutually exclusive; on the listings in the tables, some
elements are shown in parentheses to indicate that they also belong to other
groups. Copper, for example, may occur naturally as metallic copper or in the
Cu + or Cu 2 + oxidation states, the latter strongly influencing its solution chem-
istry. Thus, Cu belongs to groups 2, 4 and 5.
These geochemical groups are dominated by the oxidation states of the
elements in the Eh range of the weathering environment and consequently they
can transgress the classical groupings of the Periodic Table. This is demon-
strated in Fig. 1.5-4 by the classical group V-A elements, where Bi is in the 3 +
state and is a cation or insoluble oxide, Sb is in the 3 + state as an oxide/hy-
droxide or a weakly charged anion in the 5 + state, As is similar, further
advanced towards being an anion, and P is fully in the 5 + state as an anion.
Other classical Periodic Table groupings, such as the alkali metals, alkaline
earths, the rare earth elements and most of the group III elements (Al, Ga, In, Sc
and Y) have remained intact.
The solubilities of cations, hydroxide precipitates and anions of elements with
respect to changes in pH have the general form of U-shaped curves depicted in
Figs. 1.5-5-1.5-7, respectively. These figures together demonstrate firstly the
importance of pH and, secondly, the simple concept that cations are more
mobile at low pH and anions more mobile at higher pH. When the insoluble
elements (Fig. 1.5-5) do dissolve, they form cations in acids and anions in alkalis.
In effect, it appears that the U-shaped solubility curve moves, so that the
minimum is at:
(1) high pH values for the cations that have low charge and large size (Figs.
1.5-3 and 1.5-5);
(2) mid-pH values for more oxidized and positively charged elements that have
smaller sized ions, so that hydrolysis reactions (reactions with water; see Chapter
1.2) form insoluble oxides and hydroxides (Figs. 1.5-3 and 1.5-6);.
(3) low pH values for those elements with a high oxidation state that form
oxyanions when hydrolyzed (Figs. 1.5-3 and 1.5-7).
Of the chemical elements grouped as having variable oxidation states (Table
1.5-4), the most abundant and, in some respects, the most important, is iron. The
change in oxidation state from F e 2 + , which is soluble as a cation to F e 3 + , which
is insoluble as the oxide F e 2 0 3 , falls directly in the range of Eh and pH expected
in the weathering environment (Fig. 1.5-2). Thus, low oxidation potentials (Eh)
and low pH values (i.e. reducing, acid conditions) produce greater Fe mobility
than higher oxidation potentials and higher pH values, hence iron precipitates
TABLE 1.5-1
Elements mobile as anions, listed by oxidation state

Halide ions Elemental Oxy anions

-2 -1 0 +1 +2 +3 +4 +5 +6 +7
Te 2 " (tellurides) Te TeO, (TeO2-)
oxidizing
Se 2 " (selenides Se SeO^ (SeO 2 -)
S 2 " (sulphides) S meta-stable polysulphides, polythionates, thiosulphate etc. S0|~
(SO2")
o2- (OH) o«
Water (oxides) hydroxides
I~ iodides h
Br" bromides (Br,)
Cl~ complexes
F~ complexes
Humic compounds C C0|"
Sb 2 0 3 Sb(OH)e
As 2 0 3 AsO|"
POJ-
NH3 compounds N2 N0.7 NO3
Nb(OH)5/Nb(OH)e
TaiOH^/TaiOH)^
Mo02 MoO|-
(W0 2 ) WOf"
Te04"
Re07
Si(OH)J/SiO(OH)3
Ge(OH)J/GeO(OH)3
TABLE 1.5-2
Elements mobile as cations having + 1, + 2 and + 3 oxidation states, showing the trends in stability of some inorganic and organic complexes

Oxidation state Inorganic complexing Adsorp- Chelation by organic acids:

+ 1 +2 + 3 CI soj- co,^- tion onto humic or
goethite EDTA Fulvic oxalic
K K K K K
sol sol sol sol sol K
sol atpH
HCO;7 coj^ above
Alkali Li + low S 0.64 S s 2.79 low Li low
metals Na+ low S 0.70 S s 13 1.64 low Na low
K+ -0.7 S 0.85 S 0.8 low Κ -0.08
Rb + -0.55 S S S 0.59 low Rb low
Cs + -0.39 s
- S S 0.15 low Co low
( C u +) 2.70 -7.38
- (Cu)
( A g +) 3.31 -9.74 1.3 -11.09
-4.83
-7.22 Ag -2.4
( H g l +) -17.91 -2 -6.13 -16.05
- Hgf + -7
Tl + 0.49 -3.74 1.37
-6.41 - Tl
+
-
Alkaline Mg2 - -1 s 2.23 0.95 2.88 -7.46 8.83 3.7 Mg 3.43
+
earths Ca2 low s 2.31 -4.62 0.10 3.15 -8.35 10.6 3.8 Ca 3.00
+
Sr2 s 2.55 -6.50 -9.03 10.5 8.8 Sr 2.54
+
Ba2 -0.13 s 2.70 -9.96 2.78 -8.30 7.9 -3 Ba 2.31
+
Ra2 low s -10.37 Ra

Base ( F e 2 +) s 2.2 s -10.68 142 -5 Fe2 -3

metals Co2 + - -0.05 s 2.36 s -9.98 6.5 16.4 4.7 Co2 4.72
(Mn 2 + ) -0.04 s 2.26 s 1.80 -9.30 7.5 14.0 4.5 Mn2 3.95
Ni2 + - 0 s 2.32 s 6.7 18.2 5.3 Ni2 5.16
( C u 2 +) 0.40 s 2.36 s 6.75 -9.63
- 4.5 18.9 9.5 Cu2 6.23
Zn 2 + 0.43 s 2.38 s -10.00 6.2 16.44 5.2 Zn 2 4.87
Cd2 + 1.98 s 2.46 s -13.74 7 16.36 4.7 Cd2 3.89
(Hg2 + ) 6-7 2.5 21.5 19.6 Hg2 -10
Pb2 + 1.59 -4.78 2.75 -7.79 -13.13
- 5 17.88 6-7 Pb2 4.91
3 +
(Fe ) 1.48 4.04 25.0 -20 F e 3r 7.74
+
( A l 3 +) - adsorbs 16.7 Al(OH) 3 Al3 -6
slowly is more
in acid stable

s = soluble.
86

Table 1.5-3
Stability constants of common insoluble oxides

Oxidation state Log of stability constants of soluble complexes

2+ 3+ 4+ cr so|- CH3COO- C20|"
BeO -0.3 0.72 1.62 408
A1 2 0 3 1.51 6.1
Fe203 0.64 3.38 5.73
Mn203 0.9 1.20 -10.0
Cr20, -0.4 2.60 4.6
Ga203 0.01 6.45
(V 2 0 3 ) 1.45
ln203 2.32 1.78 3.5 5.3
Sc203 0.04 2.59 8.74
Y2O3 -0.1 1.24 1.68 5.46
REE 2 *0 ; i - 0 . 4 to 1.2 to 1.8 to 4.9 to
-0.1 2.0 2.1 5.6
Bi203 2.2 2.0
(Si0 2 )
(Ge0 2 )
Ti0 2 2.2
(Ti02+)
Sn0 2
Hf0 2 0.38 3.04
Zr0 2 0.30 3.67
Pu02 0.14 3.66
Np02 0.15 3.51
Th02 0.3 3.22 3.9 8.8
(V0 2 ) 0.26 3.42
!
REE = Rare Earth Elements.

TABLE 1.5-4
Elements having variable oxidation states; the change in oxidation state commonly causes a major
change in solubility

Cations Oxides Anions

+2 +3 +4 +5 +6
2 +
Fe Fe203
Mn2 + Mn304 Mn203 Mn0 2
[V 2 + ] v 3+3 /v 2o3 V02+/V204 vo|-
[Cr2+] +
Cr /Cr203 CrO 2 "
Mo 3 + Mo0 2 MoO|-
[W0 2 ] WO|"
As(OH)§/As 2 0 3 AsO|-
Sb(OH)g/Sb 2 0 3 SbOj-
U02 uo| +
u4o9 (U0 2 ) 3 (OH) 5 +
uo2(co3)^-
 87

TABLE 1.5-5
Ions and ionic complexes of some metals in different oxidation states

Oxidation state
0 +1 +2 +3 +4 +5 +6 +7 +8
Ru RuSO? RuS0 4 + Ru0 2
Rh Rh+/Rh02 Rh 2 + Rh 3 +
Rh203
Pd Pd2+/PdO
PdCl 2 ~ x
Os Os(OH)4 Os04°
OsOf- Os04(OH)"
Ir Ir02 IrO|-
Pt Pt(OH) 2 Pt(OH) 4
ptci2: PtCll"
Au Aii(S 2 0 3 )g- Au(OH)3
Au(OH) 3 Cr
AuCl 4
Ag Ag +
Ag(s2o3)r
AgS0 4 -
Hg AgCl J x - x Hg 2 +
Hg 2 S0 4 ° HgS04°
HgCH 3 S0 3 Hg(S203)l"
HgCH 3 S~ Hg(OH)2
HgCH 3 S 2 0 3 HgCl 2
HgCH 3 Cl
Cu Cu + Cu 2 +
CuCl 1 ^* CuS04°

when a solution comes into contact with air. Manganese behaves somewhat
similarly. However, elements such as Mo, V, Cr and W that readily oxidize to + 5
and + 6 oxidation states all show an increased solubility with higher Eh due to
the formation of oxy-anions. For U, the change in oxidation state is more
complex, with oxy-cations such as U2Of+ forming mobile species (Langmuir,
1978).
Copper, Ag and Hg can have the oxidation state of either a metal or a cation
and are included with the metals group in Table 1.5-5 or the cation group in
Table 1.5-2. All of the metals in the latter group are greatly assisted in their
mobility by highly oxidative environments associated with solutions of high ionic
strength in which soluble complexes with anions can form. However, in the
presence of sulphides, a lower oxidation potential could help mobility by the
incomplete oxidation of the sulphide allowing metastable thiosulphate and other
metastable oxysulphur anions to be present and form soluble complexes. This is
particularly relevant to Au, Ag and Hg mobility (see Webster and Mann, 1984 and
88

Anion

Bi(OH>4

4 6 8 10 12

Fig. 1.5-4. Variations in oxidation state of the classical group V-A elements.

Webster, 1984). The aqueous geochemistry of gold is discussed in detail in

Chapter V-3.

FORMATION OF INORGANIC AND ORGANIC COMPLEXES

The solubility of most cations can be increased by bonding with anions, both
organic and inorganic, to give complexes having lower overall charge. The
stability constants of many of these complexes have been measured and those
more important in the geochemical environment are listed in Tables 1.5-2 and
1.5-3. The values given are the logarithm of the stability constant of the complex,
 89

-11h 1

-12 l· j

13 I i i i i i i i i i 1 1 1
2 3 4 5 6 7 8 9 10 11 12 13
pH
Fig. 1.5-5. Solubility of cations by hydrolysis as a function of pH.

such that the larger the value the more stable is the complex. These data must,
nevertheless, be used with care. For example, a comparison of the stability
constants for sulphates and chlorides shows that sulphate complexes are more
stable, which would suggest them to be the more significant. However, because
most natural waters have higher activities of chloride than sulphate, chloride
complexes are more important for geochemical mobility. The same relative
stabilities of different cations are reflected by the solubility products (if sol ) of
each complex.
90

_J I I I I I I I I I I I
2 3 4 5 6 7 8 9 10 11 12 13
PH
Fig. 1.5-6. Solubility of various oxides by hydrolysis as a function of pH.

Organic complexing becomes important in waters in which organic materials

are decaying; the stability of such complexes is illustrated by EDTA, oxalate ion
(C2Of ~), and humic and fulvic acids in Table 1.5-2, and by oxalate and acetate
(CH3COO") ions in Table 1.5-3. Because the dissociation of these organic anions
is affected by pH, complex formation can be pH dependent. Complexation plays
an important role in the processes of adsorption, co-precipitation, humic interac-
tion and microorganism activity discussed below.
 91

ADSORPTION

Adsorption refers to the binding of elements at the solution/mineral surface.

Like solubility, adsorption is pH dependent, as illustrated by the adsorption
isotherms for some cations and anions on to a goethite (FeOOH) surface (Fig.
1.5-8). Many oxide surfaces, including goethite, hematite and the Al oxides
change from being positively charged at low pH to negatively charged at high
pH. With increasing OH - concentration, such surfaces become increasingly
negatively charged and thus more cations become adsorbed from solution. On
decreasing the pH, the reverse occurs; surfaces are more positive charged,
decreasing the adsorption of cations but increasing the adsorption of anions. The
pH at which the change-over occurs, i.e. the point at which there is a net zero
charge (pzc) can be used to give a measure of whether the surface is likely to be
negatively or positively charged at a particular pH. The pzc for various common
minerals are listed in Table 1.5-6. In natural systems, however, the surface

Fig. 1.5-7. Solubility of various anions by hydrolysis as a function of pH.

92

Fig. 1.5-8. Adsorption isotherms of divalent cations and anions (SOf , Cl , AsOf , POf , SeO§ ,
Si04 ~ and M0O42") onto goethite as a function of pH.

TABLE 1.5-6
Some point of zero charge (pzc) pH values for various common minerals and soils

pzc Reference
Amorphous Si0 2 /quartz 1.8-3.5
Feldspars (NaK)AlSi 3 0 8 2.0-2.4
Olivine (MgFe)Si0 3 4.1
Kaolinite/illite Al 4 Si 4 O 10 (OH) 8 3.3-6 and 2
Montmorillonite Na 2 Mg 2 AI j 0Si24θβο(ΟΗ)24 2.5-6 and 2
Allophanes 6-7
Augite (CaFeMg (AlSi) 2 0 6 4.5
Serpentine (FeMg) 3 Si 2 0 5 9.6-11.8
Apatite Ca 5 (P0 4 ) 3 F 4-6
Calcite CaC0 3 8.0-9.0
MgO 12.5
CaO 12.9
A1 2 0 3 6.8-9.5
Gibbsite Al(OH)3 9.5
Hematite F e 2 0 3 6.5-8.6
Goethite FeOOH 7.6-8.1
Ferrihydrite Fe 4 0 5 (OH) 2 6.9
Andosol (young soil developed on volcanic ash) 4.4
Typtic Hydrandept (humic andosol) 4.25
Oxisol (latosol or ferrallsol of humid tropics) 4.0
Typtic Gibbsihumox (gibbsitic humic latosol) 4.00
Tropeptic Eutrustox (latosol in dry savannas) 3.75
Ultisol (acrisol; red yellow tropical podzol) 3.6
Alfisol (grey podzol of warm seasonal climates) 3.3
Spodosol (podzol of humid temperate climates) 4.6
Vertic Haplustoll (brown soil of semiarid steppes) <3.5

References: 1: Parks (1967); 2\ Farrah and Pickering (1979); 3: Parfitt (1980); 4 Parks and De Bruyn
(1962); 5 Stoop (1980)
 93

properties of individual minerals are subject to interference by other compo-

nents; for example, humic substances cause the surfaces of goethite to become
more negatively charged (Tipping and Cooke, 1982). This problem of predicting
adsorption characteristics is therefore complex, but can be partially overcome by
measuring the pzc of the soils themselves (Table 1.5-6). Excellent reviews of the
behaviour of mineral surfaces in soils are given by Bowden et al. (1980), Parfitt
(1980) and Furlong et al. (1981).

CO-PRECIPITATION

Co-precipitation is the term describing the precipitation of elements from

solutions in which they would normally be soluble, as the result of the precipita-
tion of some other, more abundant element. Co-precipitation is influenced by the
same factors as solubility and adsorption, being greatest at high cation concen-
trations and high pH values, whether the cation be co-precipitating with Fe
oxides (Thornber and Wildman, 1984) or with carbonates (Thornber and Nickel,
1976) (see Chapter II. 1). The extent to which an element is co-precipitated
correlates with its solubility and adsorption properties, thereby indicating that
similar bonding mechanisms are involved (see Fig. II. 1-9). Co-precipitation of
anions is similarly influenced, with anions of low solubility and low pH favouring
greater co-precipitation. This effect is demonstrated by the co-precipitation of
sulphate and chloride with pyroaurite, carbonate compounds and the Fe oxyhy-
droxides (Thornber and Wildman 1984). At higher pH values, in which CO3" is
favoured over HCO^ in solution, pyroaurite-base metal compounds are formed,
with COf ~ exclusively occupying the anion site; however, as the pH is lowered,
other anions present, particularly SOf ~ and Cl~, occupy these sites.

CHELATION BY HUMIC MATERIALS

The strong interactions between decaying organic matter and inorganic ions
may cause either enhanced solubility or complete immobility, depending on the
molecular size of the humic material. Organic matter has the greatest exchange
capacity (about 150 to 400 milliequivalents per 100 g) of any of the soil
fractions, due to the presence of humic materials. The humic acids have adjacent
carboxylic acid or phenolic -OH groups that allow the formation of chelation
bonds with metal ions. The best known synthetic chelating agent, for which the
most quantitative data are available, is ethylene-diamine-tetra-acetic acid (EDTA).
The stability constants of the chelate compounds that EDTA forms are listed
together with a compilation of stabilities for the cations with humic materials in
Table 1.5-2. The values are expressed as log (const) for the equation:
[MA+] [H + ]
log10const =
94

where the reaction is assumed to be

HA +M 2 + = MA+ + H +
humic humic
acid complex

(M = divalent metal; A = humic anion)

i.e. the greater the constant the greater the stability of the complex. Humic
substances are commonly subdivided into three general categories, namely
humic acids, fulvic acids and humin. Humic acids are those fractions that can
be extracted into strongly alkaline solutions but are insoluble in strong acids;
fulvic acids are soluble in both acids and bases whereas humin is soluble in
neither. This separation is related to molecular size, with fulvic acid < humic
acid < humin, the latter possibly bound firmly to soil grains. Chelation of a cation
with humic material may have three effects:
(1) it may be rendered more soluble by chelation with a fulvate molecule;
(2) it may chelate with two soluble humates to form a larger molecule which
then precipitates; or
(3) it could be chelated into an immobile humin.
Fulvate molecules may be important in increasing the mobility of many
cations by attacking otherwise stable minerals. One very important example of
this is the group of chelating agents known as hydroxamate siderophors, which
are complex molecules of unknown formula produced by microorganisms within
the rhizosphere. These compounds form such strong chelates with Fe m that it
becomes mobile even in an oxidizing environment and hence may be responsible
for leaching Fe oxide minerals (Cline et al., 1983). Hydroxamate siderophors are
released by plant roots and fungi and not only do they favour the mobility of
Fe 3+ even at alkaline pH, they form solutions that can keep other metals such as
Al3+, Mn2+, Zn2+, Cu2+, Ca2+ and Mg 2+ dissolved under conditions in which
they would normally precipitate.

MICROORGANISMS

Microorganisms are ubiquitous throughout the weathering environment, par-

ticularly in association with organic matter, whether living or decaying. Their
involvement with weathering reactions is generally accepted but poorly under-
stood. They play two major roles:
(1) they accelerate the rate at which reactions take place, making use of the
energy so released. Examples include the Thiobacillus bacteria, especially T.
ferro-oxidans, that accelerate oxidation of sulphur and iron compounds;
(2) they change the conditions of the system. For example, one organism may
change the pH so that another organism can then operate in a preferred
environment to complete an oxidation reaction; the two organisms thus act
together as a symbiotic system. Alternatively, an organism may produce special-
 95

ized compounds that are capable of causing greatly increased solubility, as

described in the previous section.
Microorganisms can also derive energy by breaking down large, immobile
humic molecules into smaller, more mobile ones. Hence, metals rendered immo-
bile within precipitated humic material may become mobilized with these smaller
molecules.
Research on the humic materials accumulated on the sea floor in the north-
western Pacific Ocean has indicated peroxidase enzyme activity in Pleistocene
humic materials (Nissenbaum and Serban, 1987). It appears that peroxidase
released during cell breakdown can form very stable humic-enzyme complexes;
the enzyme is thereby able to maintain a reduced environment and aid the
stability of the humic materials.
Although the potential has been recognized, there has been relatively little
research into the role of microorganisms in weathering and geochemical disper-
sion. The scope for interdisciplinary study involving biochemistry, microbiology
and geochemistry is considerable.

ENVIRONMENTAL EFFECTS

Physico-chemical environment

The two most important factors controlling the solubility of an element are
oxidation potential (Eh) and hydrogen ion activity (pH). The oxidation state has
the overriding control of the mobility of an element in solution. However, the Eh
relationships determined for pure solutions may be distorted by the ionic strength,
pH and concentration of other ions and of humic chelating molecules. For
example, in chloride-rich solutions, metallic gold has an appreciable solubility in
the + 3 oxidation state, due to the formation of the stable AUCI4 mobile
complex. Mobilization by solubilizing reactions including hydrolysis, inorganic
complexing, and complexing with smaller organic anions such as oxalate, and
immobilization by adsorption onto surfaces of minerals with variable charge,
co-precipitation and ion exchange, are all pH controlled and respond to pH
changes in the same way. Under high pH conditions, anions are more mobile and
cations less mobile, whereas at lower pH, cations are mobilized and the anions
become immobile. When humic materials are present, however, the net effect can
be reversed because the strength of the chelated bond with the cation increases
with increasing pH, and the complexes become more stable. At higher pH, such
chelate complexes behave as anions and thus become more mobile.

Climatic environments

Regional or local climate may have a general influence on weathering mecha-

nisms. Thus, in arid environments in which soils have low humic contents,
96

WET TROPICAL
Basement rock
Humic attack TERRAIN

•Waterlogged swampy areas

Everglades
Reducing environment
Low mobility

Basement
rock stable
to chemical attack
Collection of metals Fresh water,
dissolved from up slope fast flowing
streams

ARID TROPICAL
TERRAIN

Seasonal rivers
Saline lakes or
seasonal flowing
rivers

> * >°r, * . n
Maximum leaching of
'«*/>/"' 9 * basement rocks Trace
Leach- deposition"
c (n
> ^ ' °>-QQnJr, ' solutions

Fig. 1.5-9. Schematic representations of the complex conditions that need to be considered for similar
topographies in tropical terrains in (A) humid and (B) arid climates.

inorganic reactions tend to dominate. However, in humid environments, espe-

cially in the tropics, where plant growth is prolific, the mechanisms that involve
humic break down and microorganisms become more dominant. Schematic
representations of the many factors that must be considered in order to contrast
the mobilities of chemical elements in humid tropical terrains compared to arid
terrains are shown in Figs. I.5-9A and I.5-9B. The position of the water-table, the
presence or absence of accumulated organic litter, the rate of waterflow, activity
of microorganisms, degree of salinity, access of air to the soil, topography and
many other factors need to be assessed so that the dominant chemical parame-
ters can be considered. An understanding of these parameters indicates that the
factors that influence oxidation state, pH and the formation of soluble and
insoluble complexes have the greatest significance in controlling hydromorphic
dispersion in the secondary environment.