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VI. Relationship to Soil Properties

VI. Relationship to Soil Properties

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AMORPHOUS CLAY CONSTITUENTS OF SOILS



243



and the volume and nature of the washing media; adsorption is strongly

influenced by pH (Birrell and Gradwell, 1956; Birrell, 1961a) (Table I ) .

Conventional methods for determination of the exchange capacity therefore

require some revision. Perhaps the least ambiguous method is to determine

the cation and anion exchange capacity (CEC and AEC) by equilibrating

the soil sample with a dilute salt solution containing the index ions at an

appropriate pH and then measuring the retention of these ions without

removing the excess salt by washing (Schofield, 1949; Wada and Ataka,

1958; Wada and Harada, 1969; Chichester et al., 1970; van Raij and

Peech, 1972). Most of the values described here have been obtained by

such procedures unless otherwise specified.

Van Raij and Peech (1972) determined the charge characteristics of

two highly weathered Oxisols and one Alfisol from Brazil containing gibbsite, iron oxides, and kaolinite as major clay constituents. These soils develop both pH-dependent negative and positive charges in an amount less

than 10 and 5 me per 100 g soil, respectively, for the pH range 4 to 7

and at electrolyte concentration of 0.01 N ; they exhibit a point of zero

charge at pH 3-6. Barber and Rowel1 (1972) obtained similar data for

an iron-rich kaolinitic soil. They explained the variations in charge characteristics in terms of the presence of a small permanent negative charge,

pH dependent positive and negative charge influenced by the indifferent

electrolyte concentration, and the overlap of diffuse double layers causing

a neutralization of charge. In addition to this, Atkinson et al. (1967) presented evidence for ion-pair formation on iron oxides, which would inhibit

the development of diffuse double layers. Shifts of the isoelectric point in

more than 2 pH units toward an alkaline side were found for sesquioxide

minerals with the increase both in the degree of their hydration and disordering in their structural organization (Parks, 1965).

The pH-dependent CEC also occurs for chloritized 2 : 1 layer silicates,

where permanent negative charge is blocked by positively charged hydroxyaluminum groups. Accessibility to exchange sites is restored by deprotonation of the latter on addition of base (de Villiers and Jackson, 1967;

Chichester et al., 1970). Sawhney et al. (1970) thus assigned the irreversible portion of the pH-dependent CEC to the interlayers and coatings, and

the reversible portion to organic matter, and found the pH-dependent CEC

of several acid soils to be primarily due to weakly dissociated organic matter groups. The negative charge development for imogolite, allophane, and

synthetic sesquioxides was found to be reversible (Sawhney and Norrish,

1971; Harada and Wada, 1973).

Exchange capacity data for allophane and imogolite of established purity

has been very scarce. The CEC values of 135 for allophane (Si0,/A1,03

ratio = 2.0) and 30 me per 100 g for imogolite were obtained by equili-



244



KOJI WADA AND M. E. HARWARD



TABLE I

Effects of Changing the Conditions for the Measurement and Predrying of Samples on

Cation Exchange Capacity (CEC) and Anion Exchange Capacity (AEC) Values of

Imogolite-Allophane, Allophane, Halloysite, and Montmorillonitea

Cation and anion exchange material



Changes in conditions

for measurement and

predrying of samples

Salt concentration

0.2 N

0.005 N

pH: 6.0

Cation species: N H 4

Temperature: 55'C

Predrying of sample

Evacuated over P205

Heated a t 150°C



Measured

item



CEC

CEC

AEC

CEC

AEC

CEC

CEC

CEC

AEC

CEC

AEC



ImogoliteMontallophane

Allophane

(Si02/A1203; (Si02/A1203; Halloy- morillonite

1)

2)

site



++

-



++

++

+

*

+

-



f



*

ND

-



++

*

++



**

+++

*



i



If:



f



k



ND



ND



ND

&



ND



I



If:



Referencesb



(1)

(1)

(1)

(8, 3)

(2,3)

(1)



+



i

f



i

k



ND



15)



ND

ND

ND



(5)

(5)



-



f



(4)



(5)



+,



a

- and f respectively stand for about a 20% increase and decrease, and less than

a 20% change in CEC and AEC, in comparison with their reference values, when conditions

for the measurement and predrying of samples were changed as specified in the first column

from those for the reference measurement. The reference CEC and AEC values were

measured for air-dried samples by determining the cation and anion retention from 0.05

N Ca(CH&00)2 or CaClz of p H 7.0 a t 10-25°C. N D means not determined.

References (1) Wada and Harada (1969); (2) Wada and Ataka (1958); (3) Harada and

Wada (1973); (4) Wada and Harada (1971); (5) Harada and Wacla, (1972).



brating with 0.05 N NaCH,COO at pH 7.0 (T. Henmi and K. Wada, unpublished). The CEC increases with the increasing SiO,/A1,0:+ ratio for

soil clays containing allophane and imogolite ( Wada, 1967). The point

of zero net charge was found at about pH 7 for the soils containing imogolite and allophane, while the CEC was much higher than the AEC at the

same pH for weathered pumice containing allophane with a Si0,/A120,

ratio 2.0 (Wada and Harada, 1969). The large affinity and capacity of allophanic clays for anion retention were illustrated in studies by Singh and

Kanehiro (1969) and Kinjo and Pratt (1971a,b) on nitrate adsorption

by subsoils of Andepts in comparison with other soils.

Table I illustrates the effects of changing the conditions on the CEC

and AEC values measured for materials of different clay mineral compositions. The results demonstrate the greater effect of conditions on assessing



AMORPHOUS CLAY CONSTITUENTS OF SOILS



245



electric charges of soils containing allophane and imogolite compared with

crystalline layer silicates. The data have implications to methods employed.

The observed effect of pH and electrolyte concentration on both the CEC

and AEC of imogolite and allophane (Table I) was accounted for by their

effects on the proton dissociation from and the uptake by the functional

OH groups bonded to silicon and aluminum atoms, respectively (Iimura,

1966; Wada, 1967). Wada and Harada (1969) ascribed a gradual decrease in CEC with the decreasing concentration below 0.05 N to hydrolysis of exchangeable cation, while the relatively rapid increase in CEC at

concentrations above 0.1 N were attributed to a non-coulombic adsorption

of cation-anion pairs. By analogy to coprecipitated silica and alumina, Birre11 (1961a) suggested physical adsorption of salts by allophane. There

is a clear-cut difference in the hydrolysis of adsorbed cations between

the soils containing imogolite-allophane and those of weathered pumice containing allophane with a Si0,/A1,03 ratio of 2.0. This may suggest a difference in the mechanism of development of negative charge between imogolite and allophane, and may be correlated with the absence of aluminum

in 4-fold coordination in imogolite and its presence in allophane (T. Henmi

and K. Wada, unpublished). Another possible interpretation involves the

presence or absence of overlap of diffuse double layer at lower electrolyte

concentrations as proposed by Schofield (1949) and others.

Different values of the CEC of clay materials depending on the cation

species have often been reported. The effect is more manifested for imogolite-allophane and least for montmorillonite (Table I). Since the proton

is involved in the development of its negative charge, the observed phenomenon may be interpreted broadly in terms of relative bonding energies

(strength of adsorption) between the proton and the index cation being

added. Therefore, this will vary with valence and effective radius of the

cation. Approximately, the CEC decreased in the order: Ba > Ca > K,

Mg > NH,, for imogolite-allophane, and the ratio of the lowest to the

highest CEC was 0.5 to 0.6 (Wada and Harada, 1969). Different values

of the AEC depending on the anion species were also found for imogolite

and allophane (Wada and Tsuji, 1973). The AEC increased in the order:

NO, < C1 < CH3CO0<< SO,. The much higher value for sulfate anion

was interpreted in terms of specific adsorption (Section VI, A, 2).

Quite remarkably, the CEC of imogolite-allophane and allophane was

found to increase when the temperature of the solution was raised, whereas

a slight decrease was found in the AEC (Table I). The increased CEC

at higher temperature in a neutral 1 N acetate solution, was only partly

reduced by lowering the temperature again (Wada and Harada, 1971).

It was proposed that this large CEC increase includes reactions by which

some “bound” functional groups are set free for ionization and/or by which



246



KOJI WADA AND M. E. HARWARD



an AI-OH-AI bonding is formed between two terminal AI-H,O groups

(Harada and Wada, 1973).

The effect of previous drying or heating of the samples containing imogolite and/or allophane shows another interesting feature (Table I). Egawa

et al. (1959) found that the CEC decreased remarkably for an allophane

on air-drying or heating at 105OC when the CEC was measured using concentrated, e.g., 2.5 N , NH,CH,COO and 80% C,H,OH for washing. A

significant increase was, however, found after the same treatment when

the CEC was determined with 0.3 N NH,CH,COO and 80% C,H,OH.

The data shown in Table I indicate that the negative charge could develop

on dehydration, possibly including changes in the coordination of surface

aluminum atoms. The changes of surface functional groups resulting in increase of net negative charge upon drying may also be inferred from the

changes in electrophoretic mobility of allophanic clays or more simply from

the changes in pH of allophanic soils suspended in salt solutions. Watanabe

(1961, 1962) observed that the isoelectric point of allophane with a

SiO2/A1,O, ratio of 1.11 was lowered from pH 6.8 to 4.1 by air drying.

Sadzawka et al. (1 972) observed that the pH of Chilean volcanic ash soils

suspended in 0.01 A4 Na,SO, is lowered by about 0.5 pH unit or more

when the soils were dried at 110°C.

Imogolite and allophane have weak acid properties in soils as expected

from the pH-dependence of the negative charge developed on them.

Yoshida (1970, 1971 ) confirmed this by treating allophane, imogolite, and

crystalline layer silicate clays with 1 N AlCI, and determining exchangeable

aluminum and hydrogen on these clays. All the exchange sites on allophane

and imogolite were occupied by hydrogen but not aluminum, whereas more

than 60% of exchange sites in crystalline layer silicates were occupied by

aluminum. The cation selectivity of soils in cation-exchange reactions is

markedly influenced by the nature of the cation-exchange material. Yoshida (1961) determined the ratio of exchangeable NH, to Ca after treating

the soils with 1 : 1 mixture of 1 N ammonium and calcium acetates. The

soils in which humus and/or allophane predominated gave ratios in the

range of 0.2 to 0.4, whereas those predominated by crystalline layer

silicates gave ratios in the range of 1.4 to 4.

2. Sorption of Cation and Anion



A strong sorption of certain anions such as phosphate in soils is usually

associated with amorphous ahminosilicates and hydrous iron and aluminum oxides. The reaction is primarily attributed to aluminum and iron

atoms present on the clay surface, and the high reactivity of soil amorphous

constituents is correlated with their large aluminum and iron specific surface area.



AMORPHOUS CLAY CONSTITUENTS OF SOILS



247



Recent studies of anion adsorption by hydrous iron and aluminum oxides

have shown that “specific” adsorption in addition to “nonspecific” adsorption of anions normally occurs in soils (Hingston et al., 1967, 1968). The

“nonspecific” adsorption refers to adsorption of anions by simple coulombic interaction with positive charges on Al-OH,+ or Fe-OH,+ groups, while

the specific adsorption refers to incorporation of anion in the coordination

shell of an iron or aluminum atom as a ligand. The anion thus bound cannot be displaced from the soil simply by leaching with a solution containing

a nonspecifically adsorbed anion, such as chloride. The process is strongly

pH dependent, and a maximum or inflection occurs in the adsorption maximum-pH curve at pH values corresponding to the pK values of the acid

species formed by the anion. Silicate, arsenate, fluoride, ortho-, pyro-, and

tripolyphosphates, selenite, and molybdate are specifically adsorbed. Specific adsorption of molybdate by some crystalline and amorphous soil clays

was studied by Theng (1971 ).

The high value of phosphate absorption obtained by a conventional

method (more than 1500 mg as P,O, by 100 g of air-dry soil from 200

ml of 2.5% ammonium phosphate solution at pH 7 ) has often been used

in Japan for roughly distinguishing soils derived from volcanic ash and

other parent materials. The greater role in this phosphate sorption has

recently been assigned to the dithionite-citrate soluble sesquioxidic components rather than allophane (Kato, 1970a,b; Miyauchi and Nakano, 19711.

Difficulty in obtaining and defining an adsorption maximum at a pH was

also reported for adsorption of phosphate by volcanic ash soils (Tsukada

et al., 1967; Miyauchi and Nakano, 1971). This is probably due to overlapping of the reaction with a phosphate-induced decomposition of clay

minerals and with precipitation of complex or discrete new aluminum and

iron phosphates. The rapidness of the latter reaction for allophane was

demonstrated by its transformation to taranakite-like minerals in weak acid,

ammonium, or potassium phosphate solutions (Wada, 1959; Birrell,

1961b).

3 . Interaction with Organic Conipounds



There is ample evidence which indicates that the level of organic matter

in soils is affected by the presence of amorphous inorganic material (see

Section V) . Recent advances in the study of possible mechanisms of interaction between humic and fulvic acids and soil clays have been reviewed

by Greenland ( 1971) .

The high ratio of the pyrophosphate or oxalate soluble aluminum and

iron to dithionite-citrate soluble iron and aluminum was obtained for

Podzol B horizons (Bascomb, 1968; McKeague, 1967; Blume and Schwertmann, 1969). The high solubility of aluminum and iron in the pyrophos-



248



KOJI WADA AND M. E. HARWARD



phate solution was interpreted as indicating that aluminum and iron or

hydroxy-aluminum and iron ions form organic complexes (McKeague et

al., 1971). Schnitzer (1969) explained the dissolution and precipitation

of organic matter in the Podzol A and B horizons by change in the solubility

of Fe(II1)- and aluminum-fulvic acid complexes. While 1 :1 molar

Fe(II1)-fulvic acid complexes were completely water soluble, 6 : 1 molar

Fe( 111)- and aluminum-fulvic acid complexes were water insolubIe. By

differential thermogravimetric analysis, the ironpan in the Humic Podzol

from Newfoundland who also identified as being essentially a 6 : 1 molar

Fe (111)-fulvic acid complex. In these complexes, the formation of electrovalent bonds between negatively charged carboxyl groups and positively

charged aluminum and iron ions and or hydroxy-aluminum and iron ions

was inferred from infrared spectroscopy.

Accumulation of humus constitutes one of the striking features of Andosols. It is not uncommon for the carbon content of the surface soil to be

20% within 5000 years. This occurs under a warm, humid climate and

grass vegetation, and at well-drained sites. The role of allophane and related materials in accumulation of organic matter in Andosols has, therefore, been studied by a number of investigators. Recent investigations may

be classified under the following four groups. The first is concerned with

possible effects of allophane on the action of enzymes such as protease

and amylases (Aomine and Kobayashi, 1964, 1966; Kobayashi and

Aomine, 1967). These authors pointed out the importance of protective

action of allophane against biotic degradation of organic materials which

become incorporated in the soils. The second is concerned with a catalytic

effect of allophane in an oxidative polycondensation of phenolic units,

which results in formation of stable skeletons in soil humic materials. The

greater catalytic effect of allophane and sesquioxides compared with crystalline layer silicates was demonstrated for a chestnut tannin-containing substance (Kyuma and Kawaguchi 1964) and pyrogallol (Kumada and Kato,

1970). The third possibility is that allophane acts as a source of aluminum and/or iron which form insoluble humates. The fourth is concerned

with the adsorption of humic materials. Kobo and Fujisawa (1964)

studied adsorption of humic acids extracted from soils by various clays.

Adsorption studies by Inoue and Wada (1968, 1971a,b) with an extract

of humified clover showed that allophane and imogolite have a much

greater sorption capacity than crystalline layer silicates. The importance

of this adsorption in the overall accumulation of humus was inferred from

a soil incubation experiment (Wada and Inoue, 1967).

In all these studies, the preformation of allophane in the soil has implicitly been assumed. As described in Section V, C, the importance of sesquioxidic constituents, rather than allophane, in accumulation of organic mat-



AMORPHOUS CLAY CONSTITUENTS OF SOILS



249



ter in some volcanic ash soils has been increasingly recognized. In fact, the

ratio of pyrophosphate soluble aluminum to dithionite-citrate soluble

aluminum as high as 1.0 was found for such soils in which little or no allophane was detected by selective dissolution and infrared spectroscopy (K.

Wada and T. Highashi, unpublished).



B.



PHYSICAL AND



ENGINEERING

PROPERTIES



The importance of “free iron oxide” in affecting physical properties such

as aggregate formation has often been mentioned. Deshpande et al. (1968)

subjected “red” soils to different dissolution treatments and observed

changes in the physical properties. They suggested that the acid-soluble

“active” aluminum oxide rather than iron oxide is important in aggregate

formation in red soils.

It has been established that the physical properties of soils having a

high content of amorphous clay material, specifically allophane, are unique.

Birrell (1 964) and Forsythe et al. (1969) summarized features of physical

properties of Ando soils, and Sherman et al. (1964) summarized those

of Hydrol-Humic Latosols, which were thought to contain amorphous

aluminum, iron, and titanium hydrous oxides as well as allophane.

Soils containing a high content of allophane and imogolite have low bulk

densities. Values as low as 0.25 and 0.3 were found even for such volcanic

ash soils, which contain little organic matter and develop under a temperate, humid climate (Wada and Aomine, 1973). In Hawaii, Sherman et

al. (1964) reported that the ferruginous aluminous soils have bulk densities

as low as 0.09 with an average range between 0.3 and 0.5, while the ferruginous soils have a bulk density of 0.8 to 1.0. Soils developed on the

Mazama ash in Oregon commonly have bulk densities in the range of 0.7

to 0.8.

A very high natural moisture content is a common feature of soils described above, and is associated with a very low bulk density value. The

moisture contents on an oven-dried basis for volcanic ash soils in the Kanto

district range from 80 to 180% and are mostly from 100 to 140% (Suyama

and Oya, 1965). The subsoils compared with the surface soils have high

amounts of both available or free water ( p F 2.5-4.2 or 1/3 to 15 bar)

and nonavailable or nonfree water. Water retention, liquid limit, and plasticity index show a marked decrease when the samples have been previously air-dried (Birrell, 1952; Suyama and Oya, 1965; Tada, 1969). There

seems to be a critical moisture content below which this effect of predrying

of the sample appears both for the liquid limit and plasticity limit values.



250



KOJI WADA AND M. E. HARWARD



The change is, however, not parallel, and is much more pronounced for

the liquid limit. Wells and Furkert (1972) inferred that an irreversible

change takes place in water status of natural allophane by a simple

mechanical disturbance.

The tendency toward irreversible drying of soils containing allophane

is manifested in formation of stable aggregates. Kubota (1972) found that

there is a critical pF value, which may vary in a range from pF 3 to 4,

depending on the natural moisture status of the soils. Sherman et al.

(1964) reported that the Akaka soils undergo a tremendous loss of volume

on drying and will not rehydrate. The original samples, which showed little

or no crystallinity, underwent a change of state to form crystalline gibbsite,

poorly crystallized iron oxide, and allophane after dehydration. They attributed the change of soil properties to crystallization of hydrous oxides

from the corresponding gel of cryptocrystalline materials.

The difficulty in determination of particle size distribution for volcanic

ash soils has often been mentioned. The high content of organic matter

combined with amorphous inorganic constituents in volcanic ash soils poses

a problem. Undesirable effects of H,O, treatment resulting in a partial destruction of the clay constituents were discussed by Mitchell et al. ( 1964).

Lavkulich and Wiens (1970) compared effects of H,O, and NaOCl treatments for removal of organic matter on selected mineral constituents. It

was found that NaOCl extracted more organic matter with less destruction of the oxides than procedures employing H,O,. Harris (1973)

reported that the clay yield from Parkdale soils containing considerable

amounts of allophane was 14 % less in average after NaOCl treatment

than after H,O, treatment.

Treatment of these soils at pH 10 (NaOH) or at pH 4 (HCl) after

peroxidation and washing with water and with the aid of ultrasonic or sonic

oscillations seems to have been partially accepted as a means for dispersion

of the clay fraction. The alkaline medium is used for soils in which crystalline layer silicates predominate in the clay fraction, while the acid medium

is used for those containing allophane and imogolite in substantial amounts.

Matsuo (1964) claimed that sodium metaphosphate can be used as efficiently for dispersion of volcanic ash soils as other soils in Japan, but

neither his nor other subsequently published data on highly allophanic soils

support his conclusion (Kobo and Oba, 1965; Sherman et al., 1964;

Miyazawa, 1966). Adsorption of metaphosphate in an appreciable amount

by amorphous clay constituents (Yoshinaga and Yamaguchi, 1970a) also

is a disadvantage in the use of metaphosphate at recommended concentrations such as 0.032 to 0.02 M . Kobo and Oba (1965) and Kanno and

Arimura (1967) showed that when sonic oscillation is used, the removal

of iron oxide as a pretreatment is not necessary for dispersion of volcanic

ash soils. The use of sonic or ultrasonic oscillation for mechanical analysis

has, however, some disadvantages as pointed out by Watson (1971).



AMORPHOUS CLAY CONSTITUENTS OF SOILS



25 1



Birrell (1966) proposed to indirectly determine clay contents in soils containing allophane by measuring adsorption of nitrogen, acetic acid, and

water vapor.

Aomine and Egashira ( 1968 ) tested effectiveness of various electrolytes

as flocculants for allophanic clays in comparison with montmorillonite. The

flocculation of allophane is primarily determined by the valence of anions

and that of montmorillonite by the valence of cations. This probably reflects their predominating positive and negative charges. From this observation, they proposed to use the ratio of flocculation value of CaCI, to that

of Na,SO, for differentiation of predominating surface charge of soil colloids. The values 20-30 were obtained for soil clays in which allophane

and imogolite predominated while the values 0.04-0.12 were found for

those with crystalline layer silicates or humus.

The void ratios of fine-textured volcanic ash soils are in the range from

2 to 5, and mostly from 3 to 4. These values are higher than 0.8 to 1.0

for sandy alluvial soils and 1.5 to 2.5 for clayey alluvial soils. A peculiarity

common to volcanic ash soils subjected to the standard consolidation test

is that preconsolidation load (e.g., 20-40 tons/m?) far exceeds the present

overburden pressure or even the bearing capacity (10-15 tons/m2), Since

there is no geologic evidence for this preconsolidation, one might imagine

the same effect being produced by aggregation of soil particles with allophane and related colloids, possibly through drying during weathering of

volcanic ash (Birrell, 1964; Suyama and Oya, 1965).

An anomalous compaction behavior has also been noted for volcanic

ash soils. The soil normally gives a single compaction curve with a welldefined maximum, which is primarily determined by the density and the

size distribution of soil particles. The compaction curve shows the dry

density values attained at the respective moisture contents when the soil

is subjected to the same compaction procedure. However, a volcanic ash

soil gives a variety of compaction curves, and hence, the maximum dry

density and the optimum moisture at which the former is attained varies

depending upon the initial moisture content of the sample. Kuno (quoted

by Suyama and Oya, 1965) for example, reported a variation of the maximum dry density from 1.02 to 0.58 tons/m3 in association with the corresponding variation of the optimum moisture content from 60 to 135%,

when the initial moisture content of a volcanic ash soil from the Kanto

district has been changed from 40 to 130%. Another anomaly which was

noted for the allophanic soil is that the clear maximum in the dry density

curve was attained only on the moistening cycle but not on the drying

cycle. This behavior was again attributed to the fact that allophane can

contain a relatively high amount of nonfree water and that there seems to

be no sharp boundary between the nonfree and free water. It is clear that

building structures that involve soils with allophanic materials, particularly

those disturbed and compacted, make special care necessary.



252



KOJI WADA AND M. E. HARWARD



c .



CURRENT STATUS AND



MANAGEMENT

OF SOIL



SYSTEMS



Historically, problems have been encountered in the use and management of soils high in amorphous constituents. This is true for the United

States as well as other Pacific r i d countries such as Japan and New Zealand.

The problems involve failure to recognize and evaluate the importance of

the amorphous components. Laboratory analyses either have not been

oriented to these materials or the wide range in sensitivity of the amorphous

materials to the index tests has not been recognized. To a large degree

the problems encountered involve a high degree of porosity in an undisturbed state, large water-holding capacities with the tendency for the clays

to be saturated or nearly so in nature, and rearrangement of the gel structure or matrix upon manipulation. Although not always understood, some

of the relationships to engineering properties have been at least recognized. In view of this it is somewhat surprising that soil scientists

have not done more to relate the nature and occurrence of amorphous

materials to problems of soil management which involve dispersion, flocculation, aggregation, infiltration, erosion, and landscape stability. Perhaps

this is partially due to our overzealous efforts to “clean-up” the sample

prior to the analysis and obtain data more like those of standard or reference specimens which are easier to interpret. In doing so, we may have removed or modified components so that the samples no longer reflect the

properties of the systems in situ.

A significant accomplishment toward the recognition and evaluation of

amorphous components has been made by Jones and Uehara (1973). They

have perfected techniques for transmission electron microscopy which show

the presence of gel-hulls that enclose the bridge between crystalline particles. Their success is due to a combination of factors including absence

of chemicals and use only of mild sonification for dispersion, use of holey

substrate for mounting of specimens, operation of the equipment at high

voltage and low current to minimize effects of the beam, and exposure

of an area only long enough to focus and obtain a film record. Subsequent

interpretations were then made from photo micrographs. These procedures

permitted them to detect gellike materials in aluminosilicate systems, high

aluminum soils and on quartz surfaces.

In view of previous experience with relationships of amorphous constituents to engineering properties, relationships to landscape stability are to

be expected. In a study of a watershed in the Cascade Range, Youngberg

et al. (1973) found amorphous inorganic colloids to be dominant components of readily dispersible soils which were also major contributors to

stream turbidity. Amorphous components tended to remain in suspension

in the reservoir longer than smectite clay minerals. Similar studies of a



AMORPHOUS CLAY CONSTITUENTS OF SOILS



253



watershed on older geologic formations and under a different climate indicate that samples which contain a combination of smectite and amorphous

clays tend to remain in suspension and contribute to continued turbidity

of the reservoirs (Silvernale et al., 1973). In view of current interest in

preservation of the environment and our natural resources, efforts to develop similar relationships should be increased.

VII.



Summary



There are different classes of amorphous clay constituents in soils. They

have a common characteristic due to structural randomness, but react differently in physical and chemical reactions in soils because of differences

in chemical composition and structure.

The amorphous clay constituents in soils derived from volcanic ash have

been studied most extensively and intensively, simply because they are predominating in the clay fraction and have predominating influence on the

physical and chemical properties of the soils. Considerable progress has

been made in characterization of these amorphous clay constituents, specifically allophane, imogolite, and opaline silica, by application of selective

dissolution techniques combined with physical methods as represented by

infrared spectroscopy and electron microscopy.

Amorphous constituents have a significant effect on the properties of

soils. Unique physical properties associated with these components include

high water holding capacity, slippery but nonsticky consistence, high Atterberg limits, greater values for liquid and plastic limits on undried than dried

samples, low bulk densities, high void ratios, and large preconsolidation

loads, and anomalous compaction behaviors. Some of the more important

chemical properties include ability to retain large amounts of organic matter, pH-dependent cation and anion exchange capacities, large phosphate

fixation capacities, weak strength of ion adsorption, and high pH-low base

saturation relationships. Knowledge about structure, morphology, and

charge characteristics of allophane and imogolite has provided a basis for

interpreting their effect on the soil properties which pose a number of problems in practical management and use of soil systems.

A better understanding of the processes of soil development from volcanic ash has been obtained by applying advanced methods of mineralogical analysis, and by relating the formation and transformation of the amorphous clay constituents to crystalline clay constituents and to accumulation

of organic matter.

One of the problems left to future studies is characterization of amorphous sesquioxidic constituents, which are probably associated either with

allophane or with organic matter. There are indications that these relatively



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