Published 1986

Degradation of Soil Minerals

by Organic Acids 1
KimH. Tan2

The decomposition of soil minerals by humic acids (HAs) has attracted

considerable attention since the early history of soil science. Long before
Dokuchaiev formulated his pedological concept, soil organic acids, including HAs, were expected to play an important role in the dissolution of
rocks and minerals (Sprengel, 1826). Since then, conflicting arguments
were reported as to the effectiveness of these acids in rock and mineral
weathering. Mainly due to lack of supporting experimental evidence, a
large number of scientists questioned the importance of HAs as a dissolution agent (Clarke, 1911; Fetzer, 1946; Krauskopf, 1967; Loughnan,
1969). However, an equally large number of authors can also be found in
the literature defending the role of humic acids as a weathering agent
(Graham, 1941; Van der Marel, 1949; Kononova et aI., 1964).
With the increased knowledge in HA chemistry, evidence is accumulating suggesting that humic compounds playa significant role in mineral
dissolution. Today's data indicate that the acidity and chelating capacity
of these organic acids bring about the degradation of many rocks and
minerals (Singer & Navrot, 1976; Schalscha et aI., 1967; Baker, 1973;
Schnitzer & Kodama, 1976; Tan, 1980). The subsequent release of metal
cations in the form of complexes or chelates has an important bearing in
soil formation and nutrient supply to plant roots. Not only will the
mobilization and precipitation of the metal chelates result in horizon differentiation giving rise to different kinds of soils (De Coninck, 1980;
Birkeland, 1974), but depending on stability such chelates are thought to
provide the carrier mechanism by which depleted nutrients at the root
surface can be replenished (Lindsay, 1974).
1-1

SOIL MINERALS

The inorganic fraction of soils, subject to degradation processes, is

composed of rock fragments and minerals of varying size and composition. On the basis of size, the following major fractions are generally
I

Contribution of the Dep. of Agronomy, Univ. of Georgia, Athens, GA.

Professor of agronomy, Dep. of Agronomy, Univ. of Georgia, Athens, GA 30602.

Copyright 1986 Soil Science Society of America, 677 S. Segoe Rd., Madison, WI 53711,
USA. Interactions of Soil Minerals with Natural Organics and Microbes, SSSA Spec. Pub.
no. 17.
1

TAN

Table 1-1. The six categories of soil silicates on the basis of the arrangement
of the SiO. tetrahedra in their structure.
Soil silicate

Structural
arrangement of SiO.

Nesosilicates

Separate Si04
tetrahedra

Sorosilicates

Two or more linked

tetrahedra
Closed or double
rings of SiO.
tetrahedra
Single or double
chains of SiO.
tetrahedra
Sheets of SiO.
tetrahedra
Framework of SiO.
tetrahedra

Cyclosilicates
Inosilicates
Phyllosilicates
Tectosilicates

Mineral species examples

Phenacite, olivine, garnet, zircon, andalusite,
sillimanite, kyanite, topaz, chloritoid, and
sphene
Epidote group
Beryl, cordierite, tourmaline, and axinite
Pyroxenes, pyroxenoids, and amphiboles
Serpentine, mica, kaolinite, smectite, illite,
vermiculite, and chlorite
Quartz, chalcedony, tridymite, crystobalite,
opal, alkali and plagioclase feldspars,
feldspathoids, scapolite, and zeolites

recognized: gravel (> 2.0 mm); sand (2.0 to 0.050 mm); silt (0.050 to
0.002 mm); and clay 0.002 mm). Despite the variability in composition, these fractions are mostly silicates and oxides. The soil silicates are
classified into six categories on the basis of the silica (Si0 4) tetrahedra
linkages in their structure (Table 1-1). The sand and silt fractions are
mostly neso-, soro-, cyclo-, ino-, or tectosilicates, whereas the silicate
clays belong mainly to the phyllosilicates. Phyllosilicates also occur in
sand and silt fractions, whereas feldspars belonging to the tectosilicates
are frequently found in the clay fraction. Frequently, the terms secondary
and primary minerals are used to distinguish the clays from the other
minerals. Although a number of pedologists may raise some objections to
the use of these terms, for practical purpose and convenience, this article
will apply the term primary minerals to minerals which persist in the soil
chemically unchanged from the parent rocks, and the term secondary
minerals to minerals which have been formed by the weathering of
primary minerals.

1-1.1

Weathering Sequences of Soil Minerals

The breakdown and stability of soil minerals are quite complex, and
can be studied in several ways. One method to study these minerals is to use
weathering sequences and indexes, which appear to be popular in the past. A
weathering sequence is defined as a ranking of minerals in increasing (or
decreasing) order of resistance to weathering. Weathering indexes are expressed in terms of molar ratios of elements released from the minerals, or
in terms of weathering stages, or weathering means (Jackson & Sherman,
1953). A large number of weathering sequences are present in the literature. Since it is not within the scope of this chapter to discuss weathering

DEGRADATION OF SOIL MINERALS

Table 1-2. Relative stability of primary minerals on the basis of hardness

(Hunt, 1972; Tan, 1981'.
Mineral

Scale of hardness (ease of scratching,

Talc
Gypsum
Calcite
Fluorite
Apatite
Orthoclase
Quartz

Easy to scratch with fingernail (very soft,

Just scratches with fingernail (soft,
Scratched by copper coin, not by fingernail (slightly hard,
Easy to scratch by glass, not by Cu coin (moderately hard'
Just scratched by glass (hard,
Mineral scratches glass easily (hard'
Difficult to scratch by glass, mineral scratches glass very
easily (very hard'
Difficult to scratch by glass (very hard,
Difficult to scratch by glass; mineral cuts glass
(very hard'
Very difficult to scratch by glass; mineral cuts glass
(extremely hard,

Topaz
Corundum
Diamond

Mohs' scale
1
2
3
4
5
6
7
8
9
10

Table 1-3. Weathering sequence of primary minerals according to sequence

of crystallization (Goldich, 1938,.
Minerals
Dark

Light

Olivine
Augite
Hornblende

Anorthite
Labradorite
Andesine,
Oligoclase
Albite
Orthoclase,
Microcline
Muscovite
Quartz

Biotite

Sequence of
crystallization

Resistance to
weathering

Early

Least resistant

Late

Most resistant

processes in general, only a few examples, which may have some bearing
on the topic of degradation of minerals by humic acids, will be discussed
below for illustrations. One example of a weathering sequence is the
listing of minerals in order of increasing hardness from 1 to 10, known as
the Mohs' scale (Table 1-2). The degree of hardness of most soil minerals
ranges only from 1 to 7, since minerals with a hardness> 7 (e.g., topaz,
corundum, and diamond) are relatively uncommon in soils. Quartz
(hardness = 7) is generally considered the hardest mineral in soils, and
because of this, it is the soil mineral most resistant to weathering. The
question arises as to how far this concept can be applied to weathering.
Micas have a hardness of about 2 to 3, yet they are relatively resistant to
weathering.
Another example is the listing of minerals according to the sequence
of crystallization (Table 1-3). The data in Table 1-3 indicate that the
least stable minerals to weathering, represented by olivine and anorthite,
were formed first, and have less silica than the more resistant ones. According to Goldich (1938), the Si/Al ratio of both olivine and anorthite is
1:1. The molar SiiAl ratio ofanorthite is > 2.0. In biotite and orthoclase,
the more resistant minerals on the list, this ratio increases to 3:1. This

TAN

4
Weathering Sequence
Ferromagnesians

Feldspars

Anorthite
(Ca- feldspar)

Olivine

Pyroxene

Albite
(Na- feldspa~

Amphibole

Biotite

Orthoclase
(K- feldspar)
Muscovite

Quartz

Fig. 1-1. Weathering sequence of primary minerals adapted from Goldich (1938). The direction of the arrow points to increasing stability.

weathering sequence is perhaps the most known and quoted in many

books in a slightly different version as follows (Fig. 1-1). As indicated
earlier, many other weathering sequences have been formulated. For the
reader interested in this topic, reference is made to Jackson and Sherman
(1953) and Jenny (1941).
1-1.2

Weathering Indexes of Soil Minerals

Weathering indexes are defined by Jackson and Sherman (1953) in

terms of numbers expressing the degree or rate of weathering. As stated
before, several types of weathering indexes have been devised, e. g., molar
ratios, weathering stages, and weathering means. They are less relevant
than weathering sequences in the study of mineraI'degradation by HAs
and will be mentioned briefly for completeness only.
The most used weathering index is perhaps the molar ratio, which is
the ratio of the molar concentrations of elements in the mineral or the
ratio of molar concentrations of elements released during mineral
weathering. Examples of such ratios are Si02 /sesquioxide ratios, Si02/
Al 2 0 3 ratios, Si0 2/ferric oxide ratios, bases/ Al 2 0 3 ratios, alkali! Al 2 0 3
ratios, alkaline earth/ Al 2 0 3 ratios, leaching ratios, etc. For more details,
reference is made to Jenny (1941).
The weathering stage, as defined by Jackson and Sherman (1953), is
the concentration of specific minerals associated with a given degree of
weathering. These authors indicated that one or two minerals would
dominate in any soil horizon.
The weathering mean is calculated using the formula as follows:
m

= '(ps)/'p

where m = weathering mean, p = percentage of a mineral in soil, and s

= weathering stage. The summation (') is the addition of the various p
x s values of all the minerals found in a given soil.

DEGRADATION OF SOIL MINERALS

Table 1-4. Selected physical and structural properties of minerals as related
to bonding type (Evans, 1939; Tan, 1982).
Type of bonds

Mineral
property

Ionic

Homopolar

Metallic

van der Waals

Mechanical

Strong, hard

Strong, hard

Variable

Weak, soft

Thermal

High melting
point
Low thermal
expansion

High melting
point
Low thermal
expansion

Variable
melting point

Low melting
point
High thermal
expansion

Electrical

Nonconducting

Nonconducting

Conducting

Nonconducting

Optical

Variable

High refractive
index

Opaque

Transparent

Structural

High
coordination
Moderately
high density

Low
coordination
Low density

Very high
coordination
High density

Very high
coordination

1-1.3

Crystal Chemistry and Stability of Soil Minerals

Although a large number of factors account for the stability of soil

minerals, perhaps the factors related to the structure of the mineral are of
greater importance in mineral degradation by humic acids than any other
factors discussed earlier. Mineral stability depends to a large degree on
the strength of the atoms or ions binding their neighboring ions in the
crystal lattice. Four major types of bonding forces between atoms in
crystals have been reported (Table 1-4). As indicated in Table 1-4, many
of the mineral properties vary according to bond types. The ionic and
homopolar bonds between atoms yield, in general, hard crystals with
high melting points. On the other hand, van der Waals forces give rise to
weak bonds and relatively soft crystals with low melting points.
Most of the bonds in the structure of soil minerals are ionic in nature.
In the case of soil silicates, single or several units of Si0 4 tetrahedra can be
linked together by mutually sharing the oxygen atoms, or by linkages
through cations, such as Ca and Mg. For example, in inosilicates, double
chains of silica tetrahedra can be linked together by Ca and Mg (Fig. 1-2)
as is the case in amphiboles. In tectosilicates, the Si04 and Al0 4 tetrahedra
are linked together by alkali and alkaline earth metals located in the lattice interstices. An example of the latter is feldspar. The cations acting as
the connecting linkage are considered nonframework ions, and form the
weakest spots in the crystal. Whatever the structural linkage is, it is noted
that a progressive increase in sharing of framework oxygen atoms between
adjacent silica tetrahedra generally yields the minerals more resistant to
weathering.
In terms of energy relations, the Si-O-Si linkage, called the siloxane
bond (Sticher & Bach, 1966), requires the greatest energy to form, comparesl to other cation-oxygen bonds (Table 1-5). The data in Table 1-5
show that Si-O bonds are the strongest bonds, requiring 13 164.9 to

TAN

Table 1-5. Energies of formation of cation-O bonds (Paton,1978; Keller, 1954).

Cation

Energy of formation

Si +(nesosilicates)
Si 4 +(inosilicates, single chain)
Si 4 +(inosilicates, double chain)
Si 4 +(phyllosilicates)
Si 4 +(tektosilicates)
AP+ (framework)
AP+ (nonframework)
Fe J +
Mg2+
Ca2+
H+(inOH)
Na+
K+
4

kJ mol- 1

kcalmol- 1

13164.9
13118.9
13102.1
13085.4
13030.9
7868.8
7512.7
3850.6
3821.3
3515.4
2 157.8
1349.2
1252.8

3142
3131
3127
3123
3110
1878
1793
919
912
839
515
322
299

51 tetrahedron t
weak spot

strong bonds

Fig. 1-2. Schematic linkages of silica tetrahedra. Top: Linkage of two silica tetrahedra by Ca
ion. Bottom: Linkage of several tetrahedra by mutually sharing oxygen atoms. The Si-O-Si
bond, called the siloxane bond, is a very strong bond.

13030.9 kJ mol-I for their formation. Aluminum-oxygen bonds are the

next strongest (7868.8 to 7512.7 kJ mol-I needed for formation), whereas
the bonds between nonframework cations and O2 are the weakest (1252.8
to 3850.6 kJ mol-lor 299 to 919 kcal mol-I). If the following hypothesis is
valid, that bonds requiring the greatest energy to form will also be the
most resistant to weathering attack, then the data in Table 1-5 indicate
that nonframework cation-O bonds, such as Na-O and K-O will be first
to rupture. Next in line will be the H-O, Ca-O, Mg-O, and Fe-O bonds,
while the most difficult bond to break is the siloxane Si-O-Si bond. On
the basis of a progressive increase of oxygen sharing between adjacent
silica tetrahedra, Keller (1954) ranked the stability of the silicate groups
as follows: nesosilicates < sorosilicates < inosilicates < phyllosilicates <
tectosilicates. The implication is then that tectosilicates are more resistant
to weathering than the phyllosilicates, and especially nesosilicates. This
raises many questions as to the validity of such a ranking. Potash-feldspars
(tectosilicates) are not more resistant to weathering than muscovite (phyl-

DEGRADATION OF SOIL MINERALS

losilicates). Tectosilicates include feldspar and quartz whereas phyllosilicates are mainly silicate clays. The ranking above may be valid for
stability assessments, if quartz is the tectosilicate mineral used in the
evaluation against silicate clays. However, silicate clays, being the
weathering products of feldspar, are expected to be more resistant than
the latter minerals. A ranking using specific minerals rather than group
name is perhaps less subject to questions. Using mineral species names
Birkeland (1974) suggested the following ranking: olivine < pyroxene <
hornblende < biotite < quartz. Not only does this list suggest the
presence of an increase in O2 sharing in the direction of olivine - quartz,
but it also agrees with the order of minerals listed in the weathering
sequences.

1-2

SOIL ORGANIC ACIDS

Soil organic matter consists of organisms living in or on the soil, and

a variety of compounds derived from these organisms. Numerous compounds have been isolated and identified (Tate & Theng, 1980; Flaig,
1971; Stevenson, 1967). Some of them are considered nonhumified, others
are humified material. The nonhumified substances may have been released by decay of plant, animal, and microbial tissue in their original or
in a slightly modified form. They include carbohydrates, amino acids,
protein, lipids, lignin, nucleic acids, pigments, hormones, and a variety
of organic acids. The humified materials are products that have been
formed during the decomposition process from the nonhumified constituents, and consist of a group of complex compounds, such as fulvic
acid (FA) and HA and their hydroxybenzoic acid derivatives. The latter
has been formed during oxidative degradation of the humic compounds.
For a list of the possible organic compounds found in soils, reference
is made to the many articles and books available in the literature (Gieseking, 1975; Stevenson, 1967, 1982; Shorey, 1913, 1928) and to certain
chapters in this book (chapters 4, 6, 12, and 15). The present article will
list in the following pages only organic acids relevant to the topic of the
article.

1-2.1

Nonhumified Organic Acids

Plant and animal tissues contain a large number of acids, which may
be released into the soil during the decomposition process. These acids
may range from simple aliphatic acids to complex aromatic and heterocyclic acids. A partial list of the organic acids found in soils is given in
Table 1-6. Many of these acids can only be detected by thin layer or gas
chromatography, and undoubtedly other organic acids may be present in
the soils awaiting isolation and identification.
A large number of these acids are considered intermediate products

TAN

Table 1-6. Partial list of nonhumified organic acids present in soils (Flaig, 1971;
Stevenson, 1967; Whitehead, 1964; Shorey, 1928).
Organic acid

Formula

Acetic acid
Amino acids
Ascorbic acid
Aspartic acid
Benzoic acid
Butyric acid
Cinnamic acid
Citric acid
Coumaric acid
Fenilic acid
Formic acid
Fumaric acid
Gallic acid
Glutamic acid
Hydroxybenzoic acid
Lactic acid
Nucleic acids
Oxalic acid
Propionic acid
Pyruvic acid

CH,COOH

Salicylic acid
Succinic acid
Syringic acid
Tannic acid
Tartaric acid
Vanillic acid

C.H,O.
HOOCCH,CH(NH,)COOH
(C.H,)COOH
CH,CH,CH,COOH
C.H,O,
HOC(CH,COOH),COOH
C.H,O,
C,DH,DO,
HCOOH
HOOCCH:CHCOOH
C,H.O.
HOOCCH,CH,CH(NH,)COOH
C,H.O,
CH,CH(OH)COOH
HOOCCOOH
CH,CH,COOH
CH,COCOOH
.,./'OH (1)
(C.H,)'-.....
COOH(2)
HOOCCH,CH,COOH
C.H,DO,
C,.H"O,.
HOOCCH(OH)CH(OH)COOH
C,H,O,

of plant and microbial metabolism. Some of them may have been released
into the soil as root exudates, whereas others are the result of oxidative degradation of organic matter. The low-molecular-weights organic acids
are believed to be constantly introduced to soils through natural vegetation and farming (Inoue & Huang, 1984). The concentration of these organic acids is generally very low, and depends upon the conditions in the
soil. To illustrate the magnitude of concentrations of organic acids found
in soils, the following figures serve as examples. The amount of formic
acid is usually reported to range from 0.5 to 0.9 mmol 100 g-l soil,
whereas that of acetic acid is between 0.7 and 1.0 mmol 100 g-I soil
(Flaig, 1971). Whitehead (1964) reported concentrations of hydroxybenzoic, vanillic, coumaric, and ferulic acids to amount only to 1 X 10-5
mol L -I. In an earlier investigation with paddy soils, Takijima (1960) observed that the concentration of organic acids decreased with increasing
structural complexity as follows: acetic> butyric> fumaric, propionic,
valeric, succinic, and lactic acids.
These acids may have both favorable and unfavorable effects in
plant growth. They are also expected to have a significant role in the dissolution and mobilization of elements from rocks and minerals. Acetic,
aspartic, citric, oxalic, salicylic, tannic, and tartaric acids have been used
by various investigators in the study of mineral dissolution (Baker, 1973;

DEGRADATION OF SOIL MINERALS

Huang & Keller, 1970, 1972; Schalscha et aI., 1967) with some success.
Huang and Keller (1970) noted that acetic and aspartic acids exhibited a
weak complexing capacity, whereas salicylic and tartaric acid showed a
stronger capacity.
1-2.2 Humified Organic Acids
This group of organic acids includes FA, hymatomelanic acid, HA,
and humin. The hydroxybenzoic acid derivatives derived from oxidative
degradation of the humic compounds could perhaps be grouped in this
category also. The distinction between the different types of humic compounds above is based on their solubility in acid, alkali, or ethyl alcohol.
Fulvic acid is defined as the fraction soluble in alkali and acids, whereas
HA is soluble in alkali and insoluble in acid, or water. Hymatomelanic
acid is the alcohol soluble part of HA. Humin is by definition insoluble in
water, alkali, or acid. For a discussion on problems of isolation and fractionation of these compounds as real or artificial entities, reference is
made to Flaig et al. (1975), Schnitzer and Khan (1972), and Stevenson
(1982) and to chapter 4 in this book.
The contents of FA and HA may vary considerably from soil to soil
(Tan, 1978a; Gieseking, 1975). As can be noticed from Table 1-7, large
amounts of fulvic and humic acids are present in Mollisols and Alfisols,
with HAs being generally the dominant fraction in Mollisols. In Ultisols,
the humic fraction is composed mostly of F As. Humic acids are also well
represented in the organic matter of many sediments (Singer & Navrot,
1976).
The magnitude of the data in Table 1-7 indicates that the concentrations of both FA and HA in all the soils are considerably higher than those
noted for the nonhumified organic acids. Hence, the humic substances
constitute the major portion of the organic matter in soils. For this reason,
they are perhaps generally of more importance in the degradation of soil

Table 1-7. Humic (HA) and fulvic acid (FA) contents in A horizons of some
temperate region soils (Tan, 1978a).
Na.P,O, extraction
Soil

FA

HA

FA
HA

mg100 g-l
Dubuque (Alfisols)
Grenada (Alfisols)
Marshall (Mollisols)
Tama (Mollisols)
Cecil (Ultisols)
Orangeburg (Ultisols)
Burleson (Vertisols)
Houston Black (Vertisols)

592.0
588.0
244.0
288.0
484.0
516.0
160.0
192.0

432.0
128.0
444.0
780.0
80.0
80.0
376.0
236.0

NaOH extraction
(after Na.P,O,)
FA

HA

FA
HA

mg 100 g-l
1.4
4.6
0.6
0.4
6.1
6.5
0.4
0.8

288.0
192.0
156.0
156.0
132.0
80.0
20.0

42.4
96.0
176.0
288.0
84.0
76.0
80.0
68.0

Total
FA+HA
mg100g- 1

6.7
2.0
0.9
0.6
1.6
1.1
0.3

1354
1004
1020
1512
780
752
616
516

t ND

= Not determined.

HA-Alfisols (temp.)
HA-Alfisols (trop.)
HA-Inceptisol (temp.)
HA-Oxisols (trop.)
HA-Spodosols (temp.)
HA-Spodosols (temp.)
HA-Ultisols (temp.)
HA-Ultisols (trop.)
FA-Inceptisol (temp.)
F A-Spodosols (temp.)
F A-Spodosols (temp.)
F A-Ultisols (temp.)

56.8
52.3
51.4
44.3
56.7
49.0
48.7
44.8
47.9
50.9
50.2
40.6

C
5.3
5.2
5.8
7.7
5.2
4.6
4.8
6.3
5.2
3.3
4.6
4.1

H
33.3
37.2
38.7
38.0
35.4
45.7
42.7
36.7
44.3
44.7
43.4
53.9

0
4.6
3.6
4.1
2.1
2.4
0.7
3.8
2.8
2.6
0.7
1.8
1.4

N
NDt
ND
ND
ND
0.4
ND
ND
ND
ND
0.3
ND
ND

S
6.8
ND
6.0
ND
5.7
12.0
8.7
ND
ND
12.4
12.1
10.2

Total
acidity
3.9
ND
2.4
ND
1.5
9.2
2.7
ND
ND
9.1
7.9
8.8

Carboxyl

2.8
ND
3.6
ND
4.2
2.8
6.0
ND
ND
3.3
4.2
1.4

mmolg-

Phenolic
hydroxyl

ND
ND
ND
ND
2.7
ND
ND
ND
ND
3.6
ND
ND

Alcoholic
hydroxyl

ND
ND
ND
ND
0.9
ND
ND
ND
ND
3.1
ND
ND

Carbonyl

Table 1-8. Chemical composition of fulvic (FA) and humic (HA) acids extracted from tropical (trop.) and temperate (temp.) region soils
(Schnitzer & Khan, 1972; Tan, 1982).

.....

DEGRADATION OF SOIL MINERALS

11

minerals than the nonhumified organic acids. However, this also depends
on the vegetation and the kinds and amounts of organic acids produced.
The elemental composition (Table 1-8) shows FA and HA to have
almost similar C and H contents. However, they differ significantly in N
content and total acidity. The N percentage of HA from soils of temperate
and tropical regions is almost twice that of FA. However, the total acidity
of FA is approximately two times larger than that of HA. This total
acidity, attributed mostly to the carboxyl and phenolic hydroxyl groups,
is considered the reason for the activity in cation exchange and complex
reactions. Consequently, the capacity of FA in cation exchange and chelation may exceed that of HA.
The charge characteristics of the humic substances depend upon the
extent of dissociation of the carboxyl and phenolic hydroxyl groups. At pH
< 3.0, the dissociation of the functional groups mentioned above is reported suppressed, and the humic molecule behaves as an uncharged
polymer. However, at pH values between 3.0 and 9.0 dissociation of
carboxyl groups takes place, while at pH > 9.0 the phenolic hydroxyl
groups are also dissociated. Because of this the humic molecule behaves as
a negatively charged polyelectrolyte at pH values> 3.0 (Tate & Theng,
1980). The above behavior of humic compounds agrees with results obtained by Tan (1978b), who noted that at pH 11.0 HA chelated twice the
amounts of metals than at pH 7.0. At pH 7.0, the phenolic OH groups
were apparently not fully dissociated. Complete dissociation was
achieved only at pH 11.0, increasing in this way the negative charges and
chelating sites, which explains the two times higher recovery figures of
metals noticed by Tan (1978b) from metal-HA chelates produced at pH
11.0vs.7.0.

1-2.3

Effectiveness of Organic Acids in Mineral Dissolution

The effectiveness of organic acids in mineral degradation depends on a

number of factors, among which are the concentration and chemical reactivity of the acids. By sheer concentration, it was noted earlier that FA
and HA, forming the bulk of soil organic matter, were of more importance than the nonhumified organic acids. The latter may chemically
be as effective as humic substances, but due to its presence as minor constituents, its effect could be limited by that of FA and HA (Baker, 1973;
Singer & Navrot, 1976).
On the basis of chemical reactivity the organic acids can be distinguished into two groups: e.g., (i) organic acids in which the acidic
characteristics are attributed only to the presence of -COOH groups,
and (ii) organic acids in which the acidic characteristics are attributed to
-COOH and phenolic OH groups. The first category of acids are, e.g.,
formic, acetic, and oxalic. Although they may exhibit a complexing
capacity, their effect on mineral decomposition is generally more through
the acidic (H+ ions) effect. Many display dissociation constants com-

TAN

12

R-

/I
n+
-C-O ... M

-OH
Electrostatic attraction

R--to

~n+

-0-

Complex reaction
H
0 .. H-O ..... Mn+

R-=~~~~~"""'Mn.
H

Co- adsorption

( !ridge)

Fig. 1-3. Three types of interaction between HA and a metal cation. R = the remainder of
the HA molecule, and Mn + = cation with charge n+.

parable to strong inorganic acids. The second group of organic acids include FA and HA and a number of the more complex nonhumified acids.
By virtue of the presence of -COOH and phenolic-OH groups in their
molecule, they have the advantage over the simple organic acids by being
able to exert an acidic and an interaction effect. The interaction reactions
can be in the form of (i) electrostatic (coulombic) attraction, (ii) complex
formation or chelation, or (iii) water bridging (Tate & Theng, 1980).
These reactions are illustrated in Fig. 1-3.
In the formation of chelates, the metal cation may connect itself to
more than one radical. The maximum number of bonds is, however,
governed by the coordination number of the cation. The radicals involved
may belong to the same or to different ligand groups. In the latter case,
the metal links different organic compounds to one another and, hence,
effects polymerization.
The formation of chelates can be represented by the following reaction equation:
M

+ xHA

M-HAx

[1]

where M = metal, HA = humic acid or other acids, and x = number of

moles of HA ligand. The equilibrium constant, Keq , of the reaction above
is then
Keq

= (M-HAx)/[(M) (HAY].

[2]

Conversion in log form gives

log Keq

= log (M-HAx)

- log (M) (HA)x.

[3]

Log K is called the stability constant. The higher the value for K, the
larger will be the value for log K, and the stronger the tendency for

DEGRADATION OF SOIL MINERALS

13

formation of the metal chelates. By forming organo-metal chelates, these

organic acids bring about the dissolution of primary and secondary
minerals in soils. The greater the affinity of the metal cation for HAs, and
the more stable the metal-HA chelates formed, the easier the dissolution
of the cation from the mineral structure.

1-3

DISSOLUTION OF PRIMARY MINERALS

1-3.1

Release of Cations and Mineral Stability

Although the role of humic compounds in the weathering of soil

minerals is assumed to be important, only a limited number of investigations has been conducted in this respect with HAs. Much of the work began with nonhumified organic acids (Huang & Keller, 1970, 1972b;
Schalscha et al., 1967). Using a 0.01 M solution of acetic, aspartic,
salicylic, and tartaric acid shaken with olivine, augite, muscovite, labradorite, and microcline, Huang and Keller (1970) reported a rapid dissolution of Si, AI, Fe, Mg, Ca, K, and Na from the minerals in the first 24 h.
This dissolution slowed down and reached near-constant values after 5 to
21 days. Alkaline earth elements and Si were dissolved in larger amounts
than the other cations. Where the molar ratio of released cation/Si was
1.0, Huang and Keller (1970) considered the dissolution congruent. For
the ratios> or < 1.0, the dissolution was called incongruent. Incongruent dissolution then means that the cation is dissolved more (or less)
readily than Si. Incongruent mineral dissolution appeared to be more
common than congruent dissolution.
By assuming that the cations were completely dissolved from the surface inward, Huang and Keller (1970) calculated the minimum layerthickness of dissolution for Si and AI to be in the range of 4 to 900 nm.
Microcline and augite exhibited the lowest layer-thickness of dissolution,
whereas olivine and labradorite had the largest. Perhaps this can be interpreted that among the minerals studied, microcline and augite are
relatively the most resistant and labradorite and olivine the least resistant
to attack by the organic acids. Noticing that tartaric and salicylic acid
produced a thicker dissolution layer than acetic and aspartic acid, Huang
and Keller (1970) concluded that this difference was due to the stronger
chelating power of salicylic and tartaric acid.
Recently, the use of FA and HA in mineral dissolution studies has
received more attention (Baker, 1973; Singer & Navrot, 1976; Schnitzer &
Kodama, 1976; Tan, 1980). The results suggest that these acids are equally, if not more, effective in the decomposition of primary minerals than
the group of organic acids discussed earlier. The data show invariably
that after a rapid initial dissolution, the rate of dissolution decreased and
became very slow with time, as illustrated by Fig. 1-4 and 1-5. Figure
1-4 shows the cumulative release of Si and Al from microcline by HA and
FA solutions at pH 7.0 as a function of shaking time (Tan, 1980). The con-

14

20

18

.516

~14

'e

~12

-(

-;10

a
oS

(ii

",6
E

4
2

/-

/-

.....-----

TAN

MICROCLINE

AI HA
_ FA
0
Si . 0

LSD05 " 1.05

LSD0 5"0.019

--~

...........

o-O-o-~

(.:;

- /-0-

~,-e-100

300

0 _ 0 - -0 _ 0

500

700

900

SHAKING TIME (HRS)

Fig. 1-4. Dissolution of Si and Al from microcline by HA and FA (pH 7.0) as function of
extraction time (Tan, 1980).

~.5

30
26

!
ii 22

... 18
....

.!. 14

<

.,0, "': LSD" = 0.204

x 0: F = 89.2
P < 0.001

oS

100

300 500

700

900

SHAKING TIME (HRS)

Fig. 1-5. Silicon concentrations in FA (pH 7.0), FA (pH 2.5), and water (pH 2.5) extracts of
microcline as a function of extraction time. The F value was computed with data at 21 h.
Correlation is significant at the 99 % level of probability (Tan, 1980).

centrations of the elements detected at 885 h were considerably smaller

than that reported by other authors (Schnitzer & Kodama, 1976). At 885
h, 0.035 mmol Si and 0.078 mmol Al g-l of microcline were found in the
solutions in the HA system. Using the terms proposed by Huang and
Keller (1970), this then is an incongruent dissolution. Fulvic acid effected
a smaller or weaker dissolution, since only 0.014 mmol Si and 0.011 mmol

15

DEGRADATION OF SOIL MINERALS

Al g-I of microcline were measured in the supernatants. Recently,

Kodama et al. (1983) indicated that the rate of dissolution depended on
whether the experiments have been conducted in a closed or open system.
In a closed system, Kodama et al. (1983) reported that dilute FA rapidly
dissolved substantial amounts of Si, AI, Fe, Mg, and K from biotite during
the first 100 h, after which the rate of dissolution decreased exponentially
with increased time. In an open system, the rate of dissolution was fast for
30 to 35 days, following which the dissolution rate slowed to near constancy. The ratios of elements dissolved differed from those of the
minerals in being enriched in Fe and Mg. The authors above believed that
this was an indication of preferential dissolution of elements in octahedral
coordination.
Both the acidic effect and complex or chelation reaction contributed
to the dissolution process. The data in Fig. 1-5 indicate that dissolution
was greatly enhanced by low pH. In the aqueous solution (pH 2.5), the Si
content at 885 h was almost 10 times that detected in FA supernatants of
pH 7.0. The use of FA at pH 2.5 yielded an additional increase in Si concentration. Statistical analysis, significant at the 99 % level of probability,
suggested that the increase in dissolution by the use of FA at pH 2.5 was
attributed to the interaction between acidity and chelation.
The ease of mineral decomposition by humic compounds was in the
following decreasing order:
Biotite> K-feldspar > muscovite

(Tan, 1980)

Biotite> phlogopite > muscovite

(Schnitzer & Kodama, 1976).

Such a stability sequence agrees fairly well with those discussed earlier.
Both muscovite and biotite belong to the phyllosilicate minerals. However, as expected from our structural analysis, the presence of large
amounts of nonframework cations in the structure renders biotite to be
the least resistant to HA attack.

1-3.2 Formation of Dissolution Layers

It is generally believed that as a result of attack by organic acids, the
surface of the minerals is altered and acts as a diffusion layer or diffusion
barrier. This layer is perhaps amorphous and may be composed of AI-organic complexes (Huang & Keller, 1972a; Singer & Navrot, 1976).
Further dissolution must proceed through this residual envelope and its
presence is perhaps the reason for slowing down the decomposition process with time. As indicated earlier, the depth of penetration by organic
acids may vary in thickness from 4 to 900 nm, consequently the diffusion
layer is expected to have this range of thickness. However, not much is
known yet on its existence and composition.
Using petrographic and scanning electron microscopy (SEM), the

TAN

16

present author succeeded in obtaining pictorial evidence for the existence

of the diffusion layer (Fig. 1-6, 1-7, 1-8, and 1-9). Figure 1-6 shows a
standard hornblende mineral not treated with HA. The large mineral
close to the center of the picture has a uniform blue-green color, indicative of its content of ferrous iron. After treatment with 100 to 4000 mg L-I
HA, part of the borders of the mineral became rusty brown in color, while

Fig. 1-6. Petrographic microscopy of nontreated hornblende minerals (Objective x 50) .

..

Fig. 1-7. Petrographic microscopy of hornblende after treatment with 400 mg L- ' HA (Objective x 50). Note the discoloration at the edges of the larger mineral (arrow).

DEGRADATION OF SOIL MINERALS

17

the center of the mineral remained green (Fig. 1-7). With the other primary minerals, e. g., orthoclase, apatite, calcite, muscovite, and biotite,
only in the case of calcite was the brown discoloration at the periphery of
the particle difficult to detect. The latter was due to the tendency of
calcite to disintegrate into small brown granules upon attack by HAs.

Fig. 1-8. Scanning electron micrograph of a nontreated orthoclase particle. Note the smooth,
clean surfaces of the crystal.

Fig. 1-9. Scanning electron micrograph of an orthoclase particle after treatment with 400
mg L -1 HA. Note the formation of a crust or diffusion barrier on the crystal surface.

TAN

18

Scanning electron microscopy yielded additional evidence supporting the existence of a diffusion layer. Figure 1-8 shows a scanning electron
micrograph of a clean surface of an orthoclase mineral not treated with
HA. After treatment with 100 to 4000 mg L -1 HA, the surface of the
mineral is covered by a crust (Fig. 1-9). This diffusion crust appears not
to be uniform in thickness. Measurements using several SEM micrographs
gives a layer thickness ranging from 100 to 400 nm, with the corners and
borders of the mineral exhibiting crust formation to approximately 1 /tm
in thickness.

1-4

DISSOLUTION OF SECONDARY MINERALS

Most dissolution studies of secondary minerals were conducted by

shaking kaolinite, illite, montmorillonite, and occasionally orthochlorite
and bauxite with citric, aspartic, tartaric, salicylic, and tannic acids
(Huang & Keller, 1971, 1972a, 1972b, 1972c), but seldom if ever with
HAs. As is the case with the dissolution of primary minerals, differences in
dissolution have been reported between organic acids with weak and
strong chelation capacity. Weak complexing organic acids effect mineral
decomposition more by an acidic attack. The protons dissociated by the
acids cause the surface acidity of the clay minerals to increase, and the H+saturated clay will spontaneously decompose. Brown and Miller (1971)
indicated that the protons caused the dissolution of silica. However, Bolt
et al. (1978) were of the opinion that the protons would penetrate into the
octahedral sheet, replacing the AP+ ions, which were then preferentially
adsorbed on the clay surface. The exchangeable AP+ ions in turn generated protons according to the reaction:
[4]
and mineral decomposition by proton attack was perpetuated.
Organic acids with strong complexing capacity attack minerals by
both proton attack and chelating the ion constituents of the crystal. They
appear to dissolve more of the clay minerals than the weak complexing
acids. Two to 10 times more Si and 3 to 500 times more Al were reported
to be dissolved from the minerals by the stronger than by the weaker complexing acids. The latter is in agreement with the opinion that octahedral
cations tend to be released faster than tetrahedral ions (Ross, 1967).
The rate of dissolution of secondary minerals is not much different
than that of the primary minerals. It also occurs most rapidly during the
first 24 h, after which it tapers off to reach a constant value after 45 days.
On the basis of dissolution layer thickness, as calculated by Huang and
Keller (1971), the ease of mineral decomposition is in the following decreasing order: illites > montmorillonite > Georgia kaolinite > Keokuk
kaolinite. The greatest rate of attack is 15 to 30 times more than the
smallest rate of attack.

DEGRADATION OF SOIL MINERALS

19

Table 1-9. Concentrations of Si and Al in humic acid (HA) supernatants after reaction
with kaolinite and montmorillonite (Tan, 1975).
Si

Al

JLID.o1100 g-t HA
4.8

5.9

pH 7.0:
Water extract of kaolinite
Water extract of montmorillonite
HA supernatant of kaolinite
HA supernatant of montmorillonite

Tr:j:
Tr
23.2
23.4

Tr
Tr

pH 9.0:
HA supernatant of kaolinite
HA supernatant of montmorillonite

40.7
41.8

Original HA (1.79% ash)

0.92

8.0
6.5

3.2
3.9

9.6

4.7
5.2

9.3

t The weight ratio.

:j:Tr = Trace.
Figures have been adjusted for original Si and Al contents in HA.
Using FA and HA, an almost similar dissolution rate for kaolinite and
montmorillonite was observed by Tan (1975). The difference with
previous results is that similar amounts of Si or AI were dissolved from
kaolinite (or montmorillonite) by HAs (Table 1-9). The data in Table 1-9
also show that at pH 9.0 almost twice the amount of Si is dissolved from
the minerals than at pH 7.0, but the ratio of dissolved Si to AI appears to
follow somewhat the silicon dioxide (Si0 2)/aluminum oxide (AI 20 3) ratio
of the corresponding mineral.
The decomposition of secondary minerals by humic compounds can
also be supported by x-ray diffraction and infrared analyses. The x-ray
diffraction analysis of montmorillonite before and after treatment with
FAs (Fig. 1-10) demonstrates that the main diffraction peak of montmorillonite has decreased in intensity as a result of attack by FA. Infrared
analyses of clays, separated from a Davidson soil (clayey, kaolinitic,
thermic, Rhodic Paleudults), also show reduced intensities of infrared absorption for Si-O and AI-OH vibrations at approximately 1025 and 900
cm-t, respectively (Fig. 1-10). A gradual decrease in height of the Si-O
absorption band at 1025 cm- 1 can be noticed with increased pH of the FA
solution. Statistical analysis indicates the presence of a negative correlation between absorption band intensity at 1025 cm- 1 and pH (Fig. l-ll),
significant at the 99 % level of probability. This correlation suggests that
higher pH levels create conditions more favorable for breaking the
Si-O-Si bonds in the tetrahedral sheets.
1-5

KINETICS IN DISSOLUTION REACTIONS

The dissolution process of silicate minerals in inorganic solutions is

reported to be governed by either a diffusion process (Ross, 1967, 1968),
or a first order reaction (Huang & Keller, 1972a).

20

TAN
8i

1.56nm

micrometers
(microns)

9, 10
12 14, 16
, 'i
,
Davidson soil

\V A---+FA

pH9

+FA

pH9 1~400~~~10~'0~0~--~60~'0~

Decrease of Xray dif

fraction peak heights
of montmorillonite
(air dry)

wavenumber cm- I
Decrease of infrared absorp
tion bands intensities in the
finger print region of soil clays

Fig. 1-10. Left: X-ray diffraction analysis showing a decrease in peak intensity between 1.6
to 1.5 nm of montmorillonite (air dry), after treatment with FA at pH 5.0 and 9.0. Right:
Infrared analysis showing a gradual decrease in Si-O and Al-OH absorption bands of a
Davidson clay 2.0/Lm) after treatment with FA at pH 5.0 and 9.0 (Tan, 1975).

A reaction involving the dissolution of a solid phase usually proceeds

through diffusion. The individual reacting units of atoms are firmly held
within a crystal lattice. To remove these atoms with a consequent lattice
rearrangement, the equilibrium lattice positions have to be disturbed.
Sufficient energy must be provided by the attacking acids to break the
bonds in the crystal lattice. The released units within the crystal have no
freedom of movement, but can only transfer to an adjacent vacant lattice
site. Such a reaction is called diffusion. Although the true process is still
unknown, diffusion reactions are thought to propagate through an
advancing interface, called the diffusion layer.
In acid dissolution reactions involving diffusion the data are expected
to obey the parabolic rate equation as follows:

[5]
where a = ratio of cations removed from the mineral to the total amount
initially present, k = diffusion rate constant, and t = time of dissolution.
It is apparent from the equation above, that the larger the value for k the
faster the rate of dissolution. Plotting a against ..Jt gives straight dissolution lines.

21

DEGRADATION OF SOIL MINERALS

12
Si-O infrared absorption
at 1025 cm- 1

10

E
() 8

L:

.~
Ql

~6
In

Ql

C
"0

~ 4

III

Y
df
r

= 11.97 -

=2

0.73X

= - 0.992**

pH

Fig. 1-11. Relationship between height of the Si-O infrared absorption band at 1025 cm- I of
a Davidson clay (after treatment with FA) and pH. Correlation is significant at the 99%
level of probability (Tan, 1975).

On the other hand, first-order reactions must conform to the firstorder rate law (Ross, 1967):
In (1 - a)

=-

2.303 log (1 - ex)

kt + constant or

=-

kt + constant.

[6]
[7]

When log (1 - a) is plotted against time, the dissolution curves are

straight lines.
Applying the two laws as discussed above, Huang and Keller (1972a)
indicated that dissolution of Si and Fe from illite was controlled by a diffusion reaction, whereas that of AI, K, and Mg followed a first-order rate
reaction. However, Ross (1967) reported that dissolution of Al and Mg
from orthochlorite was controlled by diffusion proceeding from the
particle edges inwards.
Since no agreement seems to exist as to the exact nature of the dissolution process of AI, the present author applied the laws above in the dissolution of microcline by HA and FA using data previously published for
Si and Al (Tan, 1980). After plotting the data (Fig. 1-12), it appears that
both the dissolution of Si and Al obey the parabolic diffusion law. The
data for Al released by HA and Si released by FA suggested a parabolic regression, which resembled closely the Mg dissolution curves presented by
Ross (1967). However, statistical analysis revealed the presence of a linear

22

TAN

35

I
.l
J
I. ~/

30

25

Si-HA
Y 1.26X - 0.18
r = 0.995* *

AI-HA
I

,V

V,'

20

)(

y. 0.82X + 1.06
r = 0.969* *

Si- FA
y. 0.55X + 1.97
r = 0.966* *

V,'
I

/ /0

15

,'0
,V

10

AI-FA

~,-r"f

~r
5

10

15

20 25

30

y= O.12X-O.OO3
r= 0.983**

Vt

(hrs)

Fig. 1-12. Fraction of Si or AI (a) dissolved from microcline by HA and FA as a function of

...ft. The calculated regression equations yield linear curves obeying the parabolic rate
equation for diffusion processes: or = kt.

regression, with a correlation coefficient Significant at the 99 % level of

probability, which are the conditions for a diffusion process as spelled out
by Ross (1967) and Huang and Keller (1972a).
The dissolution of AI by a diffusion process is more in agreement with
the concept that AI3+ ions are framework constituents of the crystal network, and may transfer from one vacant lattice site to the next during diffusion. As soon as it passes the diffusion layer, the first-order reaction may
take place. The difference between dissolution of Si and AI is in the diffusion rate constant, k. As expressed by the slope of the regression lines,
the rate constant, k, is larger for Si than for AI.

DEGRADATION OF SOIL MINERALS

23

1-6 ROLE OF DISSOLUTION PRODUCTS IN

SOIL GENESIS AND FERTILITY
By forming metal-organic complexes, humic compounds and other
organic acids may accelerate the decomposition of soil minerals. The dissolution products in the form of chelates and complex compounds have an
important bearing on soil genesis and fertility. Not only will they affect
horizon differentiation in the pedon, but they will also promote or inhibit
development of new soil minerals. Schwertmann and Taylor (1977) reported that crystallization of iron oxides was inhibited by the presence of
ferric-FA complexes, whereas transformation of hematite to goethite was
mediated by Fe-organic complexes (Schwertmann, 1971). Direct evidence
for the inhibitory effect of FA on the crystallization of iron and aluminum
hydroxides has also been presented by Kodama and Schnitzer (1977,
1980). Linares and Huertas (1971) noted that formation of kaolinite was
enhanced by the presence of small amounts of F As and perhaps their
chelates. Kodama and Schnitzer (1977, 1980) were of the opinion that the
concentration of FAs and pH had a pronounced influence on the crystallization of iron and aluminum oxides minerals. Fulvic acid present in concentrations of 5.0 g L-l was noticed to completely inhibit formation of
goethite and hematite, whereas lower FA concentrations (0.5 g L- 1) appeared to favor crystallization of the minerals above. In the absence of
FA, gibbsite was reported to be formed at pH 6, but the addition of increasing amounts of FA first delayed and then inhibited crystallization of
these minerals. These authors believe that in the form of Fe- and AI-FA
complexes, it is unlikely that crystallization will occur.
Kwong and Huang (1981) reported that tannic acid and lowmolecular-weight organic acids such as citric acid, had a similar influence
on crystallization of minerals as the humified acids. Huang and coworkers observed a structural distortion in the hydrolytic precipitation
products, including pseudoboehmite, by the use of increasing amounts of
tannic acid. In their experiments to produce imogolite, Inoue and Huang
(1984) noticed that the presence of citric acid greatly perturbed the interaction of hydroxy-aluminum ions with orthosilicic acid, thus hindering
the subsequent formation of imogolite. The soluble products formed in
the presence of citric acid were according to the authors above protoimogolite and aluminum-citrate chelates.
Current concepts on formation of spodic horizons are based on
formation of Al and/or Fe-humic chelates. Stability and mobility of these
compounds depend on the metal concentration in the soil solution. If the
amount of AI and/or Fe available for complex formation is low, complexes
will be formed in the A horizons with low metal/organic ratios. In this
case the amount of Al and/or Fe chelated is insufficient to cause
immobilization of the metal-humic compound, and may then move down

24

TAN

the pedon (De Coninck, 1980). During the downward migration, the
chelates may pick up more of the polyvalent cations, which result in a
progressive decrease of their net negative charge. The presence of a higher
metal ion concentration in the subsoil, or an acidity different from that of
the A horizon, may eventually neutralize the remaining charges and the
consequent precipitation of the chelates gives rise to the development of
spodic horizons.
On the other hand, if sufficient amounts of AI, Fe, or other metal
ions can be released by mineral weathering so that metal-humic chelates
can be formed with high metal/organic ratios, the chelates formed are immobilized in the A horizon before they can migrate down the pedon. The
formation of mollic epipedons in Mollisols is an example of such an immobilization in the form of Ca-humates. Another example is the development of A horizons rich in organic matter of Ando soils (Andepts and
Andisols), which is perhaps the result of immobilization of complexes
between humic substances and allophane and/or other alumina compounds (Wada & Aomine, 1973).
Finally, worth mentioning is the role of chelates in soil fertility,
especially micronutrient availability. Many of the cations chelated are essentially micro nutrients and can be made available to plants by exchange.
This exchange is quite different from the classical cation exchange as a
result of coulombic attraction in a double layer. The cation present in the
chelate cannot be replaced by, e.g., K+ or Na+. The latter ions are not
capable of occupying the position of a Cu 2 + ion or other transition metals
in a chelate. A chelated transition metal can only be exchanged by
another transitional metal. Depending on pH, Lindsay (1974) reported
that Fe 2 +in chelate form could be replaced with relative ease by Zn 2 +and
vice versa.
Because of chelation, Lindsay (1974) indicated that diffusion and
mass flow of micronutrient elements to roots were increased. The chelates
were thought to provide the carrier mechanism by which depleted nutrients at the root surface were replenished. Availability of chelated Fe, Zn,
and Mn was reported to be pH dependent and corresponded to stability of
the metal-organic complexes.

1-7

SUMMARY AND CONCLUSIONS

The decomposition of soil minerals by organic acids has been known

since the early history of soil science. Soil minerals subject to dissolution
are primary and secondary minerals. Their susceptibility to decomposition varies depending upon a number of factors, e. g., hardness, molecular
structures, and bonding energies. Structural bonds in a mineral requiring
the greatest energy for formation will be the most resistant to weathering
attack.
Organic acids effective in mineral dissolution are breakdown
products of soil organic matter, and consist of simple organic acids and

DEGRADATION OF SOIL MINERALS

25

complex high-molecular-weight acids, e.g., HAs. The dissolution of elements from the minerals by the simple acids is attributed more to an
acidic effect, although some evidence of chelating effects is also present.
Humic acid affects mineral dissolution by both the acidic effect and complex formation or chelation. Organic acids with strong chelation capacity
appear to be more effective in the decomposition of soil minerals.
Cations in octahedral sheets have been reported to dissolve at higher
rates than those in tetrahedral sheets. A number of lyotropic series is
available in the literature indicating a ranking of the relative amounts of
elements released. Although Al and Fe are frequently listed as exceeding
other elements in amount extracted by dilute acids, no general agreement
exists on the ease of release between the various elements.
Analysis with the petrographic microscope yields evidence for the
dissolution to proceed from the periphery towards the inner layers of the
crystal. Scanning electron microscopy shows the development of a diffusion layer on the surface of the dissolving mineral, ranging in thickness
from 100 to 1000 nm. This diffusion layer acts as a diffusion barrier and
slows down further dissolution of the mineral.
Two kinetic reactions have been suggested to account for the release
of ions, e.g., diffusion obeying parabolic rate equation and first-order
reactions. Silicon and Fe were reported to be released by diffusion,
whereas AI, K, and Mg were dissolved by a first-order reaction. However,
current results of decomposition analysis using HAs indicate that diffusion
is more important than first-order reactions.
The dissolution products in the form of chelates have an important
bearing on soil genesis and fertility. Formation of spodic horizons, mollic
epipedons, and A horizons rich in organic matter of Ando soils are attributed to mobilization and immobilization of the humic-metal chelates.
Many of the cations chelated are essentially micronutrients and can be
made available to plants by exchange.

REFERENCES
Baker, W. E. 1973. The role of humic acids from Tasmanian podzolic soils in mineral degradation and metal mobilization. Geochim. Cosmochim. Acta 37:269-281.
Birkeland, P. W. 1974. Pedology, weathering and geomorphological research. Oxford University Press, New York.
Bolt, G. H., M. G. M. Bruggenwert, and A. Kamphorst. 1978. Adsorption of cations by soil.
p. 54-90. In G. H. Bolt and M. G. M. Bruggenwert (ed.) Soil chemistry. A. Basic elements. Elsevier Science Publishing Co., New York.
Brown, D. S., and R. J. Miller. 1971. Bentonite instability and its influence on activation
energy measurements. Soil Sci. Soc. Am. Proc. 35:705-710.
Clarke, F. W. 1911. The data of geochemistry. 2nd ed. U.S. Geol. Surv. Bull. 491. U.S.
Government Printing Office, Washington, DC.
De Coninck, F. 1980. Major mechanisms in formation of spodic horizons. Geoderma 24:
101-128.
Evans, R. C. 1939. An introduction to crystal chemistry. Cambridge University Press, New
York.
Fetzer, W. G. 1946. Humic acids and true organic acids as solvents of minerals. Econ. Geol.
41:47-56.

26

TAN

Flaig, W. 1971. Organic compounds in soil. Soil Sci. 111:19-33.

----, H. Beutelspacher, and E. Rietz. 1975. Chemical composition and physical properties
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components. Springer-Verlag, New York, New York.
Gieseking, J. E. (ed.) 1975. Soil components, Vol. I. Organic components. Springer-Verlag
New York, New York.
Goldich, S. S. 1938. A study in rock weathering. J. Geol. 46:17-58.
Graham, E. R. 1941. Colloidal organic acids as factors in the weathering of anorthite. Soil
Sci. 52:291-295.
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