CHAPTER VIII

CHEMICAL EQUILIBRIA IN THE SURFICIAL ENVIRONMENT

As rocks weather, their substance is made available for erosion and dispersion away from the place
of origin. Selective solution, deposition, or sedimentation during the course of erosion and dispersion can
result in a far-reaching redistribution of the products of weathering . Redistribution is governed by the
chemical and physical properties of the various dispersed constituents and of the media within which they
move. An understanding of the chemical equilibria that determine the behavior of the chemical elements
in the surficial environment is clearly essential for effective geochemical prospecting.

The products of weathering at the earth’s surface are partitioned between the relatively immobile
solid phase that constitutes the regolith, and the mobile fluid phase made up of free-flowing underground
and surface waters. The solid phase is composed of the insoluble products of weathering, which are
dispersed by the relatively slow mechanical movement of clastic fragments. Weathering products that
either are water soluble or that occur in forms that can be readily suspended and swept along by flowing
water are dispersed more rapidly.

The mobility of the chemical elements in the surficial dispersion cycle is therefore largely controlled
by their solubility in water. Some elements, such as the Si of detrital quartz grains, characteristically
occur as components of insoluble minerals. Others, such as Na or Cl, are almost always found in the
water-soluble phase . Most elements, however, fall somewhere between these extremes. Either they are
partitioned between the two forms, or are soluble under some conditions and insoluble under others.
Empirical observations on the mobility of elements are reviewed in Chapter 2 and in the Appendix. The
following sections summarize some of the factors of the chemical environment that have an effect on the
partition of elements between the more mobile aqucous phase and the less mobile solid phase.

I. COMPOSITION OF NATURAL WATERS

The normal content and range of major and minor elements in natural fresh water are illustrated in Fig.
14.5 and Table 14.1. The total salinity (dissolved solids) depends on both climate and rock type. It ranges
from a minimum of perhaps 10 ppm in areas of cold climate and high rainfall to several per cent in warm,
desert environments. The presence of calcareous or other readily soluble rocks naturally tends to raise the
total salinity in all environments. The bulk of the solids dissolved in watter normally consists of
dissociated ions, principally , , , , , , and . To these should be added
soluble but undissociated , the stable colloidal suspensions of hydrous Fe-oxide, and the dissolved
and colloidal organic matter. Small to moderate amounts of dissolved gases ( , , , , ) are
also present (see Chapter 18). The relative proportions of the major constituents depend to a large extent
on the rocks through which the water percolates. High relative and absolute amounts of , , and
 with associated high pH values occur in waters derived from the chemical weathering of calcareous
rocks. High concentrations ranging up to thousands of ppm may occur in areas of oxidizing sulfide
minerals, Extremely high contents of and , and sometimes , , and , may result from
the leaching of saline deposits.

Variations in the major constituents affect the dispersion of the minor elements in fresh water
primarily by providing reactants, either for the precipitation of insoluble minerals or for the formation of
soluble complex ions with the minor elements. These effects are considered separately in the following
sections.

II. Eh-pH RELATIONSHIPS

Perhaps the most important of all the factors governing the solubility of a given element in water is the
relationship between the concentration of hydrogen ions in the solution, expressed as pH, and the
oxidation potential, or Eh.
A. Hydrogen-ion Concentration

This parameter is customarily expressed as the negative logarithm of the hydrogen-ion activity, for which
the symbol “pH” is used. Most natural waters have a pH between about 4 (acid) and 9 (alkaline). Near
oxidizing sulfides, concentrations of sulfuric acid may be high enough to produce a pH of 2 or even less,
and conditions more alkaline than pH 9 occur in some desert soils and lakes.

Most metallic elements are highly soluble in acid solution but can be precipitated as oxides or
hydroxides by increasing the pH. For alkali and most alkaline-earth elements, the pH of precipitation is
above the range of natural waters, but many higher-valent or transition elements are precipitated in the pH
range of natural waters. For example, may precipitate as by the following hydrolysis reaction:

for which the equilibrium constant is

where a, the chemical activity in solution, is approximately equal to the concentration in moles per liter.
By taking logs of this equation and rearranging :

or, since :
The solubility of may then be plotted against pH, as in Fig. 8.1. At pH 7, the solubility of is
mole/liter or , equal to mole/l g/mole g/l, or
g/l (14 ppb), which is approximately the content of many natural waters (see the Appendix).

In the simplest case, the solubility of determines the maximum amount of in solution; any
larger amounts will tend to precipitate as . This simple relation may be modified by other ions that
may either form complex ions of higher solubility, such as , or that react with to form
compounds with a lower solubility than , such as , in the precipitation of malachite. In addition,
varying degrees of supersaturation may exist.

Figure 8.1 shows that is very soluble under acid conditions, but that under neutral to alkaline
conditions it is insoluble. In agreement with this generalization, high contents are found in acid water
near oxidizing orebodies, but contents in normal ground waters with pH of 70-8,5 are very low,
usually 10 ppb or less.

Fig 8.1. Solubility of as a function of pH, showing limitation by .

Table 8.1
Solubility of metal oxides and hydroxides

Saturation Ph
Compound Ion Log
( M ion)
* Source: Wagman et al. (1968), Truesdell and Jones (1974), and Langmuir and Whitte-more (1971)
* Reactions are of the type:
,

,
Table 8.1 summarizes the solubilities of some simple oxides which can be precipitated by changes in
pH. As can be seen from the pH values at which mol/l may be dissolved, the oxides and hydroxides
of , , , , and are relatively soluble in the pH range of natural waters, and, for
practical purposes, precipitation of oxides and hydroxides does not limit the solubility of the metal. For
, , , , and , the oxides and oxyhydroxides may limit the solubility in a few very
alkaline environments. In the case of , , , and , the oxides and hydroxides exert a very
important control in natural waters. For other ions and elements, such as , , , , ,
, and , the solubility of the simple ions is so low as to be of no significance in natural waters.
These relationships are closely related to the overall mobility of the elements in surface processes
(Section II of Chapter 2).

B. Oxidation-Reduction Potential
A second very important control on mobility of elements is the concentration of electrons in the
environment, called the oxidation-reduction or redox potential. This factor is important because many
elements occur in more than one valence or oxidation state, and the properties of elements both in
solutions and solids change considerably from one valence to another. For instance, occurs in minerals
and natural waters as and , and more rarely as metallic . Other elements with more than one
valence state in nature include C, N, S, V, Cr, Mn, Cu, As, Se, Mo, Sn, Sb, W, Hg, and U.

For many purposes, the concentration of electrons is most conveniently measured and expressed as
the Eh, a voltage measured between a platinum electrode and a standard hydrogen electrode immersed in
the solution (Langmuir, 1971: Garrels and Christ, 1965). In the convention generally used in
geochemistry, a high Eh indicates an oxidizing system, and a low Eh a reducing system. Many chemists
use the same scale but with the signs reversed.
Measurement of Eh and chemical calculations involving Eh can be illustrated by a simple cell
involving a electrode placed in a solution of 1 M and 1 M (or, more precisely, a solution
with unit activity of and . A hydrogen electrode (platinum in contact with hydrogen at 1 atm is
also placed in the solution. The measured voltage between the electrodes is 0,337 V, produced by the
following reactions at the electrodes:
copper electrode:
hydrogen electrode:
The electrons furnished by the reaction of to flow through the connector and are utilized to reduce
to metallic .
If the measured concentration of in solution differs from 1 M, the measured Eh follows the
relation:

Where is the standard reaction potential of the cell (0,337 V in this case) with all reactants and
products in their standard states, is the gas constant (1,98 cal/deg-mole), is the absolute temperature
( ), is the number of electrons transferred in the oxidation-reduction reaction (two in this case), and
is the Faraday (23,06 cal/V). For the general oxidation reaction involving reactants B and C forming
products D and E:

where is the chemical activity of the species and is the reaction quotient. In the example above,
metal is in its standard state, so and:
At 25 C and using logs to the base 10:

Figure 8.2 shows the application of these equations to the solubility of . Under reducing
conditions, the solubility of is very low, and is in solution as , but under more oxidizing
conditions, solubility increases and predominates.
At the surface of the earth, atmospheric oxygen is the most abundant oxidizing agent. Environments
with access to the atmopshere or to downward percolating waters saturated with oxygen are normally
oxidizing. As access to free or dissolved oxygen decreases because of depth below the surface or impeded
flow of oxygenated surface waters, the environment becomes progressively less oxidizing and more
reducing. Carbonaceous material produced by plant or animal life furnishes the principal reductant in the
surficial environment. Where carbonaceous matter has accumulated and access to the atmosphere is
restricted, strongly reducing conditions are found.

C. Eh-pH Diagrams

Because Eh and pH are such important variables, many aspects of the mobility of elements are clearly
expressed in Eh-pH diagrams, using these

Fig. 8.2. Solubility of as a function of Eh, showing limitation by metal.

two variables as axes. The simplest diagrams are those involving H, O, and the element in question.
Boundaries between solid phases can be calculated from equations like the following for the system:
 Values for can be calculated from the relationship , , using free-energy values
tabulated by Wagman et al. (1968, 1969, 1971), Truesdell and Jones (1974), Naumov et al.
(1974), and other reference books. Garrels and Christ (1965) describe methods for calculating Eh-pH
diagrams and show examples of their use.

A diagram for the system - - is shown in Fig. 8.3. A unique line separates pairs of solids, but an
arbitrary concentration of the dissolved species must be selected to locate boundaries between solids and
dissolved species. A value of M is conventionally chosen for most major and minor elements,
because solubilities greater than this value generally are significant geochemically. However, for the less-
abundant elements, values of M and even less may be appropriate. Equations 8.4 and 8.7, as
graphed in Figs 8.1 and 8.2, are used to calculate the limit of significant in the figure.

The Eh and pH of some natural environments are summarized in Figs 8.4 and 8.5. The upper slanting
line marks conditions oxidizing enough to decompose

Fig 8.3. Eh-pH diagram for system at and 1 atm. Lines labeled , ,
indicate molarity of dissolved . The dashed line separates fields of dominantly from dominantly
.

water to (1 atm) and . The lower slanting line is a similar limit for conversion of to (1 atm).
As noted previously, natural environments containing organic matter and isolated from the atmosphere
fall near the lower limit of water stability. These include waterlogged soils, euxinic marine, and similar
environments. Where atmospheric oxygen is readily available, as in rain, streams, and surface ocean-
water, measured Eh and pH values fall in the upper part of the diagram. Actually, if the water is saturated
with oxygen at 0-2 atm, the oxidation potential is very close to the upper limit of water stability, but both
dissolved and gaseous oxygen react so slowly that neither Eh electrodes nor most chemical reactants can
sense this higher oxidation potential. Instead, they sense less-oxidizing conditions created by the
intermediate product (Sato and Mooney, 1960). In

Figure 8.4. Approximate position of some natural environments as characterized by Eh and pH. (From
Garrels, 1960.)

general, the measurement of Eh is fraught with great difficulties in most natural waters, and an accurate
value is very difficult to obtain (Morris and Stumm, 1967).

D. Forms of Sulfur and Carbon in Solution

Among the relatively abundant components of natural waters are sulfur and carbon. As illustrated in Figs
8.6 and 8.7, the form taken by these elements in solution varies widely, depending on the pH and Eh. The
mobility of many other elements is strongly dependent on the abundance and form of C and S, because of
the insolubility of many carbonates, sulfides, and sulfates.
 The major dissolved species for sulfur are , , , and . In addition, S is relatively
insoluble in acid solutions and may precipitate as the element under intermediate oxidation conditions.
The size of the wedgeshaped field of native S decreases with decreasing dissolved S; at M dissolved
S , the field extends only to about pH 3. In the (aq) field, the pressure of g) in
atmosphere is approximately equal to the activity of (aq) in solution, and the gas tends to escape to
the atmosphere, making such solutions unstable unless contined. In typical fresh waters, dissolved S is in
the range M, but near oxidizing sultide deposits or in brines, much higher values are normal.

Fig. 8.5. Eh and pH values of mine waters. Oxidized ore zone; () primary ore zone. (From Sato and
Mooney, 1960)

In the oxidizing region, the stable carbon species are , , and . The relative amounts
of each of these species can be evaluated from the equilibria:

The pressure of in the atmosphere is normally about atm, from which the amounts of
each of the above species in aerated waters can be calculated for any given pH. In soils and most ground
waters, is higher, commonly from atm to atm, as a result of oxidation of organic
matter. Under reducing conditions, graphite and organic C compounds
Fig. 8.6. Eh-pH diagram for sulfur species. Light labeled contours indicate pressure of in atm. Total
dissolved sulfur M.
Fig. 8.7. Eh-pH diagram for carbon species.

become stable (in contrast to their metastability in contact with normal air), and species such as methane
have appreciable equilibrium pressures, as evidenced by the release of bubbles of methane (“swamp gas”)
from organic muck in lakes and swamps.
The oxidation-reduction reactions of S and C species tend to be very sluggish, but bacteria and other
organisms are able to catalyze the reactions and use the energy in their metabolism. The abundance of the
reduced species tends to depend on the activity of bacteria as much as any other factor.

III. FORMATION OF COMPLEXES

Although most metallic elements occur in acid solution as simple ions , , , a wide variety
of complex hydroxy- and oxyons are formed in more alkaline solutions. Complexes may also be formed
in solutions containing other anions, especially those with which the cation forms a compound of low
solubility. For example, forms the complexes , , , , , ,
, , and others. Figure 8.8 illustrates the proportions of different forms of in solution
considering only the complexes with and , for two values of . The partition between two
forms is found from equilibrium expressions such as:

In the complexes described above, the anion forms only one bond with the cation and is termed
unidentate. However, some more complex anions can occupy several of the coordination sites around a
metal cation. For example, the oxalate ion is bidentate:

Formation of such multi-dentate complexes is termed chelation, and the resulting affinity between the
ions tends to be stronger than in unidentate complexes.
Fig. 8.8. Distribution of species in solution as a function of pH at . (a) with atm;

(b) with atm.

IV. SOLUBILITY OF MINERALS

The solubility of minerals places an important restriction on the mobility of elements, as indicated in the
previous section. If perfect chemical equilibrium always existed, the solubility would be an absolute
upper limit for the concentration of an element in a natural water. However, supersaturation and related
non-equilibrium phenomena can lead to concentrations higher than the equilibrium values.
Supersaturation is most evident for minerals of very low solubility. For example, the low solubility of
hematite and goethite can limit concentrations to very low levels in oxidizing waters, but in some
waters, ohserved concentrations are higher than the equilibrium solubility by a factor of more than
(Langmuir and Whittemore, 1971). Instead of the stable goethite or hematite, these waters precipitate a
metastable amorphous -oxyhydroxide with much higher solubility, which only slowly recrystallizes to
the more stable crystalline forms, with a concomitant decrease in solubility. The very fine grain size of
most -oxyhydroxides also tends to increase their solubility. In contrast to the large factors of
supersaturation observed for insoluble minerals, the more soluble minerals tend to nucleate more readily
and recrystallize to coarse crystals so that supersaturation is not so marked. On the other hand, an
mineral with an equilibrium solubility of M that is supersaturated by a factor of is only
supersaturated by 5·6 ppb, but that is supersaturated at M is supersaturated by 4000 ppb.
Thus, for many geochemical purposes, the solubilities are an effective limit on the mobility of elements in
natural waters.

A wide variety of minerals other than metals, oxides, and hydroxides can limit the mobility of
elements. For example, malachite is more common than tenorite in the
oxidized zone of deposits, and anglesite , and cerussite are common oxidized
minerals. In reducing environments, sultides are highly insoluble. For trace elements, the least soluble
mineral may be rare or unrecognized, so that a very complete knowledge of possible solids is necessary to
predict limits on mobility. The true limit of equilibrium solubility can be far lower than the inferred one,
if the correct mineral phase is not known, but the least soluble known mineral does give an upper limit.

The concentration level at which a precipitation of a mineral can control an element depends on the
concentration of all components of the mineral, so that the solubility product must be used to determine
the equilibrium concentration of the element. For example, for the reaction
A typical content of in fresh waters is 30 mg/l, or mole/l. At this level of sulfate, the
maximum solubility of is given by:

Considering that the normal content of in natural waters is , as

indicated in the Appendix, natural waters are undersaturated in anglesite by a factor of about 1000.

However, anglesite is not the least soluble mineral at all values of . As illustrated in Fig. 8.9,
cerussite is less soluble at values of about and above. The precise relations are determined by the
content of carbonate species and the amount of sulfate, as well as the . In normal stream waters at 8
and higher, values are limited to about the observed range of background values. In most other
environments, much higher values are possible, but note that dissolved contents in oxidizing ores
are limited to about M, and the dilution with normal waters will rapidly deplete this to background
levels away from the orebody.

Fig. 8.9. Solubility of minerals in the system - - - - at , 1 atm under oxidizing conditions,
atm (typical of soil and ground water) at two levels of total sulfur. (cerussite) and

(anglesite) are stable phases; (hydrocerussite) is nearly stable. Dashed lines

show metastable solubilities.
 The effects of , , and other constituents can be depicted on – diagrams by selecting a value
for the total content of the additional element, as was done for Fig. 8.9. For example, choosing a value of
M for total dissolved , and a pressure of , Fig. 8.10 shows the fields of mobility
( M) and solubility as a function of and . Note the large area in which is very
insoluble in the reducing portion of the diagram, as well as the area of . If the dissolved content
for mobility is decreased to M, for example, the fields of the solids will contract and the fields of the
ions will increase.

The mobility of some trace elements may be controlled in indirect – effects. Hem (1977)
showed that the and contents of many natural waters were consistent with precipitation of and
at the and conditions set by equilibrium between -oxides and dissolved . This redox
couple is common in many waters of intermediate oxidation state.

Fig 8.10. – diagram for the system - - - - , atm (oxidizing region only),

M, , 1 atm. In hatched area, is relatively immobile.

 V. ADSORPTION AND ION EXCHANGE ON COLLOIDAL PARTICLES

Another major process governing the mobility of trace elements in the surfcial environment is adsorption
and ion exchange onto colloidal particles, which have diameters in the range - A( -
cm), and consequently have a large surface area for adsorption (Fig. 6.2). Iron and manganese oxides and
hydroxides, organic matter, clays, and silica are the most common natural materials occurring as colloidal
particles. Initially, the ions adsorbed on surfaces are in active equilibrium with the surrounding solution,
but with time, the adsorbed ions may move into lattice sites or become overgrown by the solid. Under
favorable conditions small amounts of colloidal materials can scavenge important amounts of dissolved
elements from solution. Upon flocculation of the colloidal particles, the originally dissolved element is
immobilized in soil or stream sediment or as a coating on a mineral grain (Jenne, 1977).

Most adsorption and exchange is caused by electrical charges on the surfaces or in the lattices of
colloidal particles. Two types of charge distribution may be distinguished: materials having fixed charge,
primarily the clay minerals; and those of fixed surface-potential, such as the - and -oxides (von
Olphen, 1963).

A. Ion Exchange in Clay Minerals

Montmorillonite and vermiculite clay minerals have an inherent excess of negative charge in their
silicate layers because of substitution within the silicate lattices. Illites and mixed-layer clay minerals
share this type of charged lattice, but the amount of charge (exchange capacity) is considerably less than
for montmorillonites and vermiculites. Cations enter the interlayer exchange sites in clay minerals only by
exchanging for a cation already in the interlayer sites in order to maintain an electrically neutral state of
the entire clay particle. Exchange of ions follows the following pattern (Wahlberg et al., 1965);

where –clay, -clay, and -clay indicate the clay mineral with , or in the exchange sites.
In natural waters, clay minerals contain a mixture of ions in the interlayer sites.
Although the ratios of ions in the exchange sites can be estimated from the equilibrium constants for
reactions like those listed above (Maes et al., 1975), the amounts of various ions held in exchange sites
are also dependent on the exchange capacity. Some values of exchange capacity for clay minerals and
other natural materials are listed in Table 8.2. Montmorillonite, vermiculite, and organic matter have
much larger exchange capacities than other materials, and if present, dominate the ion-exchange
properties of the sediment or soil. A commonly observed sequence of increasing replacing power of the
common simple ions on clays is
In general, ions of higher valence are more strongly held in exchange sites than those of low valence, with
the prominent exception of hydrogen ion

Table 8.2
Exchange capacity of some clay minerals and common soils*

Cation-exchange capacity
Minerals and soils
(mEq/100 g)*

Kaolinite 3-15
Halloysite 5-50
Montmorillonite 80-150
Illite 10-40
Chlorite 10-40
Vermiculite 100-150
Organic fraction of soils 150-500
Podzolic soils (U.S.A.) 5-25
Chernozem (U.S.S.R.) 30-60
Black cotton soil (India) 50-80
Latosol (Zambia) 2-10
Gley soil (Zambia) 15-25

* Source: Jorfe (1949), Grim (1953), Mohr and Van Baren (1954), Tooms (1955), and Govett (1958).
* Milliequivalents per 100 g.

B. Adsorption on Surfaces
The surface charge of oxides, hydroxides, organic materials, and other types of colloids with constant
surface potential results from ionization of surface atoms, or from chemical adsorption of dissolved ions
onto the surface. For example, the on the surface of a -hydroxide tends to dissociate in a manner
analogous to other weak acids:

where the is part of the mineral structure and is on the surface. The surface thus acquires a
negative charge (Parks, 1965). By dissociation of adsorbed watcr molecules, oxides form charged
surfaces in a similar manner.
 The extent of dissociation of surface or depends on , as shown in Fig. 8.11, and as
predicted from eqn 8.24. For -oxides, dissociation at 7 is extensive, and the surface of most
natural colloidal -oxides and -hydroxides has a strong negative charge. Under very acid conditions, an
excess of is adsorbed to the surface, and it has a positive charge. At about 3, the surface is
uncharged. This is termed the zero point of charge (ZPC), The lack of charge near this allows
particles to closely approach each other and flocculate into larger particles which settle out. Because the
charge on the surface is controlled by and in solution, these ions are termed potential-
determining ions.

Fig. 8.11. Schematic diagram of surface charge on - and -oxides, as a function of .

For -oxides, the ZPC is - , so that natural -oxides are usually positively charged (Parks and
de Bruyn, 1962). Organic colloidal particles are usually negatively charged. Adsorption onto colloidal
oxides, hydroxides, silica, and organic materials is also controlled by the number of charged sites, and
charge balance may not be maintained. For cxample, adsorption of and other divalent cations onto
-oxides takes place by a one-to-one exchange of ions (Murray, 1975a):

The surface charge thus depends on the , concentration in solution, as well as on (Murray,
1975b), and is another potential-determining ion.
Adsorbed ions can occupy several types of sites on or near a charged colloidal particle. In solution,
most ions are accompanied by a shell of water molecules held by electrostatic attraction for the
dipole (Fig. 8.12a). Charged colloidal particles are surrounded by a cloud of oppositely charged hydrated
ions (counterions) attracted by the charged surface (Fig. 8.12b). Exchange of these electrostatically
attracted ions with the surrounding solution takes place rapidly and easily, with only minor discrimination
between ions. The attraction of such ions by predominantly electrostatic forces is termed non-specific
adsorption. At the zero point of charge, these ions are not adsorbed, as in the case of on -oxide
(Fig. 8.13a).

Fig, 8.12. (a) Schematic diagram of dissolved cation with strongly bonded inner shell of molecules
and weakly bonded outer shell; (b) weak, non-specific adsorption in which attraction is predominantly
electrostatic; (c) stronger, specific adsorption in which outer molecules and possibly some inner
molecules are displaced, and chemical bonds may be operative.

Some ions, especially those of higher valence or more complex electronic structure, such as the
transition metal ions, are more strongly attracted to the surface of colloids and lose part or all of their
envelope of water molecules (Fig. 8.12c). Chemical bonds specific to the ions and the surface may be
operative. This process is termed specific adsorption. , , , and, to a lesser degree, other
divalent ions show this behavior on -oxide, as demonstrated by significant adsorption at the zero point
of charge (Fig. 8.13).

Fig. 8.13. Adsorption of divalent cations on as a function of . (a) Alkaline earths; (b) transition
metals. Cation concentration M. (After Murray (1975a). Reprinted with permission from
Geochim. Cosmochim. Acta, © Pergamon Press Inc., 1975.)

The amount adsorbed can be expressed by the equilibrium constant for the adsorption reaction; for
example, for eqn 8.25:

where is the activity of adsorbed on the surface of the , and is the activity of
surfaces with undissociated on their surface. If the activity of with undissociated on its
surface is considered to be relatively constant, then eqn 8.26 may be rearranged to give:
where and are the molar concentrations of dissolved and adsorbed . Experimental data
commonly follow this type of relation (Fig. 8.14), which is called a Kurbatov plot.

Fig. 8.14. Kurbatov plots for the alkaline earth metal ions on -oxide. Metal concentrations M.

(After Murray (1975a). Reprinted with permission from Geochim. Cosmochim. Acta, © Pergamon Press
Inc., 1975.)

As indicated by the above relationships, the amount of adsorbed , which at low concentrations is
proportional to , is dependent on the following factors:
(i) The activity of ions in the surrounding solution (taking account of any complexing).
(ii) The of the surrounding solution.
(iii) The energy of bonding, as expressed by the equilibrium constant.
(iv) The number or density of adsorption sites, as expressed in the example by .
(v) In more complex cases, the activity of other ions competing with and for the sites.
The energy of adsorption varies from one ion to another, as suggested by greater adsorption for some
elements than others, given similar concentrations in solution (Fig. 8.13). The relative strength of
adsorption for some elements on -, -, and -oxides and hydroxides is summarized in Table 8.3. In
general, divalent ions are more strongly sorbed than univalent ions, and transition metals more than non-
transition metals. Well-crystalline materials may show different adsorption preferences than amorphous
or poorly crystalline solids (Kinniburgh et al., 1976).

Table 8.3
Relative affinity for adsorption of some cations*
Humic
-oxides Amorphous Goethite Amorphous Substances
 -oxides -oxides (1) (2)
Greatest

Least

*Source: -oxides, Murray (1975a); amorphous - and -oxides, Kinnburgh et al. (1976); goethite,
Forbes et al. (1976); humic substances, (1) Schnitzer and Hanson (1970), and (2) Gamble and Schnitzer
(1973).
All ions in solution compete for adsorption sites on the surfaces of colloidal particles, and the
equilibrium population of adsorbed ions is a composite of many adsorption reactions like eqn 8.25. At
near-neutral , where is at low concentrations, or may be the most important ions
competing with trace elements for adsorption to the surface of particies, and exchange reactions may be
more conveniently written with rather than as the competing ion. Complex ions may also be
adsorbed. There is some evidence that hydroxy complexes of ions (such as ) are more strongly
adsorbed than simple ions (Stumm and Morgan, 1970).
Experiments show that specific sorption is generally not completely reversible. The amount of an ion
adsorbed follows the simple relations described above as a cation is added to the solution, but when the
amount in solution is decreased, only part of the expected amount is desorbed (Fig. 8.15). Ions initially in
exchange sites apparently become permanently fixed in oxides and other phases. Possible causes for this
behavior are diffusion of the adsorbed ion into a lattice site, recrystallization of the oxide to leave the
adsorbed ion within the lattice rather than on its surface, and loss of coordinating water molecules so that
the ion is directly bonded to the surface. Drying of colloidal phases is one way of accomplishing the last
process. The adsorption properties of dried samples may be very different from the original natural
sample.
Among the factors determining the abundance and nature of adsorption sites are the mineralogical
identity of the particle and its crystallinity Amorphous oxides generally have the largest surface area per
unit mass. The several polymorphs of -oxide and -hydroxide (pyrolusite, birnessite, todorokite, etc.)
diller in adsorption properties. Further differences are expected from the non-stoichiometric nature of
many oxides. For example, Murray (1975a) experimented with a hydrous phase of stoichimetry ,
Recrystallisation and dissolution precipitation of colloidal - -oxides can have major effects on
adsorbed elements (Jenne, 1968).

Fig. 8.15. Adsorption-desorption results with changing for -oxide exposed to solutions of
M . (After Murray (1975a). Reprinted with permission from Geochim. Cosmochim. Acta, © Pergamon
Press Inc., 1975.)

In clay minerals, dissolved ions may be adsorbed to sites on the edges of the sheets. The amount
adsorbed to these sites is subordinate to interlayer, adsorption in montmorillonites and vermiculites, but
predominates over interlayer adsorption in kaolinites and some illites. Figure 8.16 shows the extent of
adsorption of on kaolinite, presumably on the broken bonds of the edges of sheets. A dependence on
both and content of the solution is observable. Adsorption of and on illites by this process is
extensive enough that most of these trace elements can be transported in adsorbed form in a solution with
% suspended illite (O'Connor and Kester, 1975).
Table 8.4 shows the relative enrichment of certain minor elements in - and -oxides. In a parallel
manner, the limonite of gossans and hydrous oxide precipitates in surface drainage channels tends to
become preferentially
Fig. 8.16. Adsorption of on kaolinite as a function of pH and concentration of the solution. (After
Heydemann (1959). Reprinted with permission from Geochim. Cosmochim. Acta, © Pergamon Press Inc.,
1959.)

enriched in many minor elements. Figure 8.17 shows the relation of and to in the active
sediments of the Colden River, Isle of Man. No known sulfide mineralization occurs in this drainage
basin, so that the and now occurring with the almost certainly represent enrichment from normal
background concentrations. The same association of many minor elements with and is observed in
soils. Figure 8.18 shows the correlation of with in soils over unmineralized rocks in Zambia. Jenne

Table 8.4
Concentrations of some minor elements in iron oxide and manganese oxide sediments*
Content in average Content in Fe-oxide Content in -oxide
crustal rocks sediments sediments
Element (ppm) (ppm) (ppm)
*Source: Krauskopf (1955) and Table 2.7.

Fig. 8.17. Relation of and to in modern stream sediments of the Colden River, Isle of Man. Data
on 80-mesh fraction. (From de Grys, 1959.)

Fig. 8.18. Relationship between and in soils from Zambia. Data on 80-mesh fraction. (After Jay,
1959.)
(1968) has reviewed evidence showing that - and -oxides are major controls on the content of ,
, , and in soils and waters.

VI. ORGANIC MATTER

Organic matter is a major constituent of some soils, stream sediments, and natural waters, and is present
in at least traces in most such materials. Because of its unusual properties compared to other natural
materials, even trace amounts of organic materials can have important effects on the chemistry of trace
elements. These effects include complexing of trace ions by dissolved organic matter, resulting in
increased mobility of the element; adsorption or formation of organic compounds, resulting in
immobilization; and reduction to lower valence states, with resulting changes in chemical properties.

Organic matter normally constitutes less than % by weight of soils and stream sediments, but
reaches much higher abundances in some environments, especially in the A horizon of some soils and in
relatively stagnant or waterlogged zones, including the bottom sediment of many lakes. Natural waters
contain mg/l of dissolved organic , averaging about mg/l, compared to an average of
mg/1 of inorganic solutes (Stumm and Morgan, 1970, p. 283; Beck et al., 1974; Livingstone, 1963;
Reuter and Perdue, 1977).
Many types of organic compounds have been recognized in natural materials. The distribution and
nature of these is evidently very complex (Swain, 1970; Cranwell, 1975). Major types of natural organic
compounds include the following:
(i) carbohydrates
(ii) hydrocarbons
(iii) alcohols, organic acids, fats, waxes
(iv) amino acids, proteins
(v) humic substances
(vi) porphyrins, vitamins, pigments, and other complex compounds.

Most of these compounds are found in or associated with living organisms. The exceptions are the humic
substances which are degraded and modified from organic matter in living organisms.

A. Simple Organic Compounds

Some basic building blocks for organic materials are illustrated in Fig. 8.19. Carbohydrates with the
formula include sugars, such as glucose, and larger molecules, such as cellulose, a

polysaccharide. Hydrocarbons composed only of and include aliphatic (chain-type ) compounds like
methane, ethane, etc., and aromatic (ring-type) compounds, like benzene. Alcohols have an
substituted for an , as in methyl alcohol and phenol. Organic acids contain the carboxyl group
( ). Examples are acetic, oxalic, and citric acids. Amino acids contain an amine group ( ) and
a carboxyl group attached to an organic radical of simple or complex form.

Fig. 8.19. Some organic compounds and groups.

Metals may be bound to organic matter in several ways. Organic acids containing , , or
similar groups may form organic salts in which the metal occupies the place of the ionizable . This
type of binding is generally of moderate strength. The metal may be bonded directly to carbon atoms,
forming organometallic compounds, or to , , , or or other electron-donating atoms in an organic
compound. Bonding is generally strong in such compounds. In many organic compounds, the metal is
chelated, that is, it is bonded to two or more sites on the organic molecule, as for in hemoglobin, and
various metals in EDTA complexes (Section III of Chapter 3). Chelated metals are generally very
strongly bound (Martell, 1971). Metals may also be electrostatically attracted to the vicinity of charged
colloidal particles. This attraction is usually relatively non-selective and weak.
Some organic acids have considerable chelating power for metals. Silicate minerals are dissolved and
mobilized much more rapidly in solutions of citric, salicylic, tannic, and other acids than in inorganic
acids of the same pH (Huang and Keller, 1971). Similar increases in solubility of , , , , and
are reported (Ong et al., 1970). Lichens acquire nutrients from their substrate by attack with a complex
organic acid, and fungi produce citric and oxalic acids. The concentrations of organic acids in pore
solutions of soils range from about M for simple organic acids such as acetic, to M for aromatic
and amino acids (Stevenson and Ardakani, 1972). The movement of and out of the surface horizons
of soils probably involves chelation by organic acids.
B. Humic Substances

Although much detailed chemical work has been done on traces of the above types of organic compounds
in natural materials, the bulk of organic material in most soils, sediments, and natural waters is probably
composed of humic substances. However, because of their molecular complexity, these materials have
proven less easy to understand. Humic substances are dark-colored, acidic, complex organic materials of
high molecular weight that lack the specific chemical and physical characteristics of simple organic
compounds (Schnitzer, 1976). They form by the degradation of plant materials and from synthetic
activities of microbes (Gamble and Schnitzer, 1973). They range in molecular weight from several
hundred to perhaps several thousand (compared to less than a few hundred for compounds discussed
above), and contain predominantly aromatic (ring-type) components. Humic substances are divided into
three groups: humic acids, which are soluble in dilute alkali ( ) but are precipitated on acidification
of the extract; fulvic acids, which remain in solution on acidification of the alkaline extract; and humin,
which is the humic material insoluble in both dilute base and acid. The three types are similar chemically,
with the fulvic acid tending to be lower in molecular weight and having a higher content of ,
, and groups than the other types. Figure 8.20 illustrates a partial chemical structure of a
fulvic acid, based on the types of compounds found on partial breakdown of samples. The abundant
and groups give the humic and fulvic acids their acid properties, and are also active in
adsorbing, complexing, and chelating metals. When dissolved in water, the fulvic and humic components
are typically negatively charged (Gamble and Schnitzer, 1973). Humic substances are a complex mixture
of components, so that

Fig. 8.20. A partial chemical structure for a fulvic acid. (After Gamble and Schnitzer (1973), Reprinted
with permission from “Trace Metals and Metal-Organic Interactions in Natural Waters” (P. Singer, ed.),
© Ann Arbor Science Publishers, 1973.)
chemical and physical properties are those of mixtures rather than simple compounds.

Humic substances are estimated to constitute % of the dissolved organic matter in river water,
and to occur in concentrations of mg/l, equivalent to molar concentration of about -
(Reuter and Perdue, 1977). The humic substances in water exist in particles ranging from about μm
to greater than 1 μm in diameter. The smaller particles can be considered as dissolved, but an arbitrary
under limit must be set to distinguish these from colloidal materials. Particles less than μm are
usually considered dissolved, because easily usable filters are available at this size, but many colloidal
materials are included as dissolved using this definition. A variety of processes, including decreases in
and increases in total ionic concentrations, or in concentrations of cations capable of neutralizing the
charge on the complex, can decrease solubility of the colloidal material and cause precipitation. Humic
materials can also occur as coatings on particles of clay, soil, or sediment, and because of their large
surface area, have effects out of proportion to their mass.
Reactions of humic and fulvic acids ( ) with metals are probably of the following types:

or the overall reaction

where is a divalent ion in solution, and the and are large molecules of humic acid which
dissociate in dilute solution and behave as dissolved constituents at low values of metal content and
acidity. At higher metal contents, the humic units tend to flocculate into large chains and networks,
becoming immobilized.
Fig. 8.21. Bonding of metal in humic substances by chelation. (After Gamble and Schnitzer (1973).
Reprinted with permission from “Trace Metals and Metal-Organic Interactions in Natural Waters” (P.
Singer, ed.), © Ann Arbor Science Publishers, 1973.)
Experimental work indicates that metals are bound in humic substances both by chelation (multiple
bonds) and by complexing to a single site on the molecules. A probable type of chelation reaction is
indicated in Fig. 8.21. The relative of bonding varies the following order for typical humic substances
(Gamble and Schnitzer, 1973):

The above sequence represents the average relative bond strength on some fulvic acids, but because
the metals are bound in many different types of sites on the organic compounds, no single equilibrium
constant can describe the process: the values are merely averages for a specific level of metal content.
Individual sites on a humic substance may have very different affinities for metals, depending on the
character of the compound, the , the presence of competing ions, the content of the ion in question, and
other factors.
Chlorophyll and hemoglobin are examples of organic compounds in which metals are strongly
chelated by four organic groups. Porphyrins containing , , and other elements have similar structures
in which the metais are strongly bonded and effectively immobilized. Organic compounds containing
are thought to form strong bonds with this element in some environments (Schmitt-Colerus, 1967, 1969).
Fig. 8.22. Relation of carbon content to extractability of in soils from Zambia Data on 80-mesh
fraction. (After Govett, 1960.)
As an example of the effects of complexing and immobilization by organic matter, Fig. 8.22 shows
the clear relationship of extractable to organic content of soils in Zambia. In stream sediments,
shows a similar correlation with organic content (Rose and Keith, 1976). The amount of adsorbed on
the organic matter of stream sediments, peats, and other natural materials follows the general relation

as determined by Szalay (1964) and illustrated in Fig. 8.23.

The opposite effect, namely mobilization of elements by formation of humic complexes, has also
been documented (Rashid and Leonard, 1973; Bondarenko, 1968). In most instances this mobilization
occurs by complexing of the metal, thereby increasing its solubility, but Ong and Swanson (1969) report
that colloidai acquires a coating of organic material which transforms it into a stable colloid which is
then capable of mobility. In typical natural waters, about half of the is expected to occur in
complexes with fulvic acid, even given the competition by major cations (Reuter and Perdue, 1977).
Fig. 8.23. Adsorption of to peat, showing strong adsorption at low concentrations of , with an
enrichment of times in the peat. At higher concentrations, all the adsorption sites are filled. (After
Szalay (1964). Reprinted with permission from Geochim. Cosmochim. Acta, © Pergamon Press Inc.,
1964.)

VII. ELECTROCHEMICAL DISPERSION

In general, ground waters and pore solutions at depth in the earth are relatively reducing compared to
oxygenated waters near the surface. As a result, a vertical gradient in electrochemical potential ( ) exists
near the surface of the earth. The steepest gradient is commonly near the water table, above which
gaseous oxygen may be present in pore spaces.

Sultide ore minerals, graphite, and a few other materials of metallic luster are good conductors of
electrons compared to silicates, carbonates, and most oxides. These natural conductors tend to “short-
citcuit” the usual gradients in electrochemical puotential. Near orebodies, the high conductivity of the ore
depletes electrons from the deep environment and supplies them to
Fig. 8.24. Schematic diagram of oxidizing orebody, showing flow of electrons and ions.

near-surface regions (Sato and Mooney, 1960). The top of an orebody is thus negatively charged relative
to its surroundings, and the bottom is positively charged. Figure 8.24 illustrates the flow of electrons and
ions in and near a conducting orebody, where the orebody acts as a conductor connecting two
electrochemical cells of differing oxidation potential. Oxidized substances approach the upper end of the
orebody, receive electrons, and are reduced. Sato and Mooney (1960) suggest that the most common
reactions here are:

At the deep end of the orebody, reduced substances are oxidized by loss of electrons to the orebody:

Metallic cations such as , , or may be released at depth in the ore by this process. In order
to maintain charge balance at the two ends of the conductor, a current equal to the electronic current must
be carried by migration of ions. Cations must migrate upward and anions downward. Govett (1973a) and
Bolviken and Logn (1975) have suggested that around massive base-metal sulfide deposits, part of this
current is carried by base-metal cations ( , , ) which are electrochemically driven upward
from the ore where they may be fixed by adsorption or precipitation and give rise to anomalies, which are
observed to occur even in post-ore till and alluvial deposits above massive sulfides. However, Webber
(1975) suggests that the rates of ionic migration by this electrochemical process are much slower than
solution flow, and that the mechanism may not be very effective. Although electrochemically driven
dispersion clearly occurs, further research is needed to clarify the magnitude of such dispersion.

Electrochemical effects are also important at a more detailed scale during oxidation of sulfide ores.
The minerals stable at the lowest values, such as sphalerite and galena, tend to be oxidized
preferentially relative to those stable at higher , such as pyrite and chalcopyrite (Shvartsev, 1976).
The use of electrical surveys to identify conducting minerals and map their distribution has attracted
considerable recent attention. Electrochemical effects constitute at least part of the basis for these surveys,
which are therefore closely related to geochemical exploration (Angoran and Madden, 1977).
VIII. SELECTED REFERENCES ON CHEMICAL EQUILIBRIA IN THE SURFICIAL
ENVIRONMENT

General Garrels and Christ (1965)

Stumm and Morgan (1970)
Mortvedt et al. (1970)
Hem (1970)
Marshall (1964)
Adsorption James and MacNaughton (1977)
Parks (1975)
Metal complexes Baes and Mesmer (1976)
Sillen and Martell (1964, 1970)
Smith and Martell (1976)