ANION INFLUENCE ON SOME SOIL

PHYSICAL PROPERTIES

by
R . D . KREBS, G. W . THOMAS, AND J. E. MOORE

Virginia Polytechnic Institute, Blacksburg, Virginia

ABSTRACT

Addition of HCI, H2S04, and HsPO4 to montmorillonite clay and a montmorillonitic soil
had little effect on the liquid limit of these materials over a wide range of concentrations.
The liquid limit of a kaolinitic soil clay Was reduced markedly by both HCI and H2SO~,
whereas HsPOa decreased the liquid limit value at lower concentrations and increased it
at higher ones. These results are discussed in light of the charge variability and of anion
retention by the kaolinitic soil.

INTRODUCTION
Permeability, compressibility, and strength of fine-grained soils are related
closely to clay mineral type and to the nature and amount of adsorbed
ions and water. In the past, these factors often have been thought of in
terms of the Gouy-Chapman diffuse double-layer model of ion adsorption
on a charged surface (Lambe, 1953, 1958). Such relationships generally are
consistent with the results of research on montmorillonitic clays saturated
with monovalent cations (Warkentin, Bolt, and Miller, 1957). Recent work
on other ion-clay systems suggests that there are many exceptions to the
dicta of the double-layer theory (Aylmore and Quirk, 1959). Indeed, in
predominantly kaolinitic soils of widespread occurrence in the southeastern
United States, the double-layer theory apparently does not apply in even
a qualitative sense. This study is concerned with the effect of anions on the
properties of such a soil as compared to some montmorillonitic materials.
An hypothesis that the concentration and species of adsorbed anion
will substantially influence the physical properties of acid, kaolinitic soil
is reasonable in light of its anion-adsorbing nature. The Gouy-Chapman
theory predicts that a clay will adsorb cations and exclude anions. Where
this is the case, as with certain montmorillonite-salt solution systems,
there is a striking influence of cation species on clay physical properties
(Falconer and Mattson, 1933), whereas the anion influence is not great.
260
 INFLUENCE ON SOME SOIL PHYSICAL PROPERTIES 261

In the kaolinitic soil studied, there is an adsorption of anions as well as

cations (Thomas, 1960). These differences are shown schematically in Fig. 1.
This diagram indicates that in acid, kaolinitic softs there is an increase
in anion concentration as the clay surface is approached. Preliminary data
leading to that conclusion have been obtained in tMs laboratory. Bolt
and Warkentin (1958) have shown that the net negative charge on a clay
is the sum of the cations held and the anions repelled. In kaolinite, the net
negative charge would be approximated by the difference between the
Cloy
Surface

t
I)

#, Anion ~
(Acid Red Soil) ~ . . . . Equilibrium
c
o Solution

nion (Theoretical)

Distance From Surface---,-

FIGUREl.--Sehematic diagram of theoretical ion adsorption by clay and anion
adsorption by acid, kaolinitic (red) soil.

amounts of cations and anions held. In conjunction with this view, the p H
of a kaolinitic system has a profound effect upon the net negative charge.
Sehofield (1939) and Mattson (1927) have shown that oxide-containing
kaolinitic soils may actually possess a net positive charge at low pH values.
Quirk and Theng (1960) have shown that in montmorillonite, induced
changes in negative charge greatly alter the quantity of adsorbed water held
by the clay against an applied force. Hence, one would expect the water-
holding capacity and allied physical properties of kaolinitic soil to vary with
changes in negative charge and in the anion species adsorbed.

MATERIALS AND METHODS

To test these ideas, a simple laboratory test correlating well with a
number of soil physical properties was selected. This is the liquid limit or
upper plastic limit test as devised by Atterberg and modified by Casa-
262 NINTH NATIONAL CONFERENCE 01~ CLAYS AND CLAYMINERALS

grande (1932). The commonly employed empirical testing procedure defines

liquid limit as the water content at which a standard groove of uniform
size cut in a soil will close a distance of 89in. under 25 blows obtained by
dropping the sample cup 1 cm in a standard testing device. Compressibility
usually increases with liquid limit (Lambe, 1951). Bayer (1948) has noted
a linear correlation between liquid limit and moisture equivalent. Lambc
(1953) has suggested that the liquid limit approximates an upper limit of
"immobilized" water. This is borne out b y the data in Fig.2 indicating
i , i J

600

I 400

~_ 200
._ ,O Ca
J /
OAI

o6 2~ 4'0 6'o ab Koo

Meosured Thickness of Double Layer(~)
FIGURE2.--Liquid limit (percent H~O)versus measured thickness of double layer for
homoionic Wyoming bentonite saturated with sodium, calcium and aluminium.

a close correlation between liquid limit and double-layer thickness in

Wyoming bentonite. The liquid limit values for Ca- and Na-saturated
montmorillonite are taken from White (1955), and the double-layer thick-
ness was estimated from anion exclusion measurements following the method
of Lutz and K e m p e r (1959).
Materials used in this study were: an acid, Red Podzolie subsoil derived
from granite and known as the Cecil series; a montmorillonitic soil derived
from diabase and known as the Iredell series; and Wyoming bentonite, a
commercial montmorillonite clay. The first two materials were taken from
well-known sites in the central Piedmont of Virginia and the bentonite
from Upton, Wyoming. The soils were ground and passed through a 40-mesh
sieve before using, but no other t r e a t m e n t was imposed. The Cecil soil was
essentially M-saturated, whereas the Iredell was saturated with Mg and
Ca. The bentonite was Al-saturated with AIC13 and washed free of Cl with
 INFLU]~]NCE ON SOME SOIL PHYSICAL I)ROI~ 263

water. Chemical a n d p h y s i c a l p r o p e r t i e s of these m a t e r i a l s are given in

Table 1.
L i q u i d l i m i t was d e t e r m i n e d a f t e r a d d i n g various concentrations o f
either HC1, It2SO 4 or H a P O a a n d curing for t h r e e d a y s a t a w a t e r content
close to t h e liquid limit. Curing t i m e s of m o r e t h a n 24 h r were found to
h a v e a negligible effect on t h e results. R e p r o d u c i b i l i t y of the results (repli-
cate values were g e n e r a l l y w i t h i n 3 p e r c e n t of one another) was enhanced
b y e m p l o y i n g a single o p e r a t o r a n d t h e same e q u i p m e n t t h r o u g h o u t t h e
testing p r o g r a m .

TABLE I.--CREMICALAND PHYSICALPROPERTIESOF EXCHANGE~-ATERIALSUSED

Exchangeable Cations Clay Min. 1

Exchanger C.E.C. Liquid Plastic Plasticity
A1 Ca l~Ig K K M V Limit Limit Index

Secil 4.18 3.54 0.10 0.40 0.14 80 -- 20 75.5 43.1 31.4

[redell 16.74 0 5.20 11.36 0.18 20 80 -- 71.5 34.2 37.3
Wyoming 90.0 90.0 -- - lO0 -- 134
Bentonite

1 K = Percent kaolinite and halloysite, ~V[= percent montmorillonite, V = percent

dioctahedrM vermiculite with interlayer aluminum.

RESULTS AND DISCUSSION

F i g u r e 3 shows t h a t t h e a d d i t i o n of sulfate or p h o s p h a t e ions in the form
of acids has no influence on t h e liquid l i m i t of a l u m i n u m - s a t u r a t e d W y o m i n g
b e n t o n i t e e x c e p t a t v e r y high concentrations. Conceivably, a t high concen-
t r a t i o n s of acid, t h e h y d r o g e n is replacing m u c h of the a l u m i n u m on t h e
exchange c o m p l e x b y m a s s action. The p r o p e n s i t y of p h o s p h a t e to r e a c t
with a l u m i n u m w o u l d enhance such r e p l a c e m e n t in t h e case of the phos-
phoric acid. Because of t h e looseness w i t h which H + is held, t h e p r o b a b l e
result of this r e p l a c e m e n t is to enhance w a t e r a d s o r p t i o n a n d cause a cor-
r e s p o n d i n g increase in l i q u i d limit, as w h e n o t h e r m o n o v a l e n t cations are
a d d e d t o m o n t m o r i l l o n i t e (White, 1955).
The influence oI a c i d a d d i t i o n s on the liquid l i m i t of I r e d e l l soil, an alka-
l i n e - e a r t h - s a t u r a t e d m o n t m o r i l l o n i t i e m a t e r i a l , is shown in Fig.4. E a c h
curve was d e t e r m i n e d in replicate a n d each p o i n t shown in F i g . 4 is a n
average of four or five d e t e r m i n a t i o n s . A considerable s c a t t e r of points was
given b y t h e r e p l i c a t i o n ; far m o r e t h a n w i t h t h e o t h e r materials. The in-
flections seem to be reproducible, however.
W i t h reference to t h e effect of H~SO 4 a n d HC1 on the liquid l i m i t of t h e
I r e d e l l soil, t h e r e are a n u m b e r of possible reactions, all m o r e or less tenable.
The initial decrease in liquid l i m i t m a y be due to all a p p e a r a n c e of t r i v a l e n t
a l u m i n u m in t h e system. This m a y replace t h e exchangeable alkaline e a r t h s
w i t h a r e s u l t a n t decrease in liquid l i m i t (see Fig. 2). S u b s e q u e n t lowering
264 NINTH NATIONAL CONFEttENCE ON CLAYS A N D CLAY MINERALS

of pH m a y cause the adsorption of hydrogen on the exchange as in the

case of the bentonite with a resultant dispersion. The final downswing in

SO
H2SO" 4D 9
ON
32

-J HCI

J
60
t , t I I II I I~t I ! I I ! :111
1.0 I0.0 tO00
meq per IOOg
FIGURE 4.--Liquid limit (percent H20 ) of IredeU soil after additions of HCI, H~S04
and HaP04.

160

0 I50

140
O ~ 0 9

9-J 130 D D H2SO 4

:J

-J 120

II0
1 I [ I I I I I I I ] J I J i i I i
,/o I0.0 I000
meq per IOOg
Fra(~RS 3,--Liquid limit (percent H~0) of Wyoming bentonite after additions of
H~S0 4 a n d H a P 0 4.

the curves probably represents a procedural difficulty. At such high anion

concentrations, oven drying of water content specimens fails to remove the
water of crystallization associated with the react/on products and gives
erroneously low liquid limit values. The reactions that occur are probably
 IN~UE~C~ ON SOME SOIL PHYSICALPROPERTIES 265

more a function of cation than anion behavior. The anion effects seem to be
restricted to their influence on the availability and replacing power of
cations, as in the case of the partially ionized phosphoric acid and the ability
of phosphate to remove aluminum from the system.
A sizeable decrease in liquid limit with anion addition to the acid, kao-
linitic Cecil soil is shown in Fig. 5. I n this case replicate determinations
agreed very closely. These decreases are difficult to explain on the basis
of cation effects alone, but are closely associated with a decrease in net
negative charge that occurs when acids are added to the soil. Table 2 shows
this change in charge in relation to p H change. Note that with Iredell soil
a rise in pH has little effect on net negative charge even though the increase
i i i i i t I i ii I i I i I I II~

/
~ 4 D ~ ~ O/

i 9

--
J
ro ~~sod~]~
~
J

I,
I I I I I I III
I0.0
I
\
l) I I I I 1111
I00,0
meq per IOOq
FIGURE5.--Liquid limit (percent H~0) of Cecil soil after additions of HC1, H2SO4
and HaP04.

with Cecil soil is nearly linear. Associated with the kaolinite in Cecil soil
are polymers of hydroxy aluminum and iron which exist mostly as clay
coatings. Anion adsorption and pH-dependent charge often h a v e been
observed for softs containing these polymers (iVlehlich, 1950; Mattson,

TABLE 2.--EFFECT OF P H ON NET I~EOATIVE CHARGE

pH Iredell Cecil
(meq/100 g) (meq/100 g)
2.4 20.0 1.40
3.3 2.00
4.3 19.9 2.60
5.2 19.9 3.24
6.1 4.40
CO~ 18
266 NINTH NATIONAL CONFERENCE ON CLAYS AND CLAY MINERALS

1927). Apparently, the amphoteric nature of the noncrystalline hydrous

oxides intensifies the charge variation which is present to some extent in
pure kaolinite (Schofield and Samson, 1953).
It is not known whether the negative charge reduction in kaolinitic soils
is due to the creation of positive charge sites as proposed by Taylor (1959)
or whether it is a result of the suppression of hydrogen ionization from
OH groups. The latter theory seems tenable in the case of soils containing
an abundance of hydroxy aluminum and iron polymers. Lowering the p i t
would naturally have the effect of suppressing hydrogen disassociation, but
it might also remove the hydroxyl in question from the system by its
reaction with hydrogen to form water. In this case, the hydroxyl might be
replaced with the added anion forming an aluminum or iron basic salt
polymer. Such "ion penetration" has been described by Rollinson (1956)
for hydroxy aluminum polymers in solution. Ion penetration, more or less
reversible, is plausible for SO~-, occurs less easily with CI-, and is difficult to
visualize in the case of H2P04-, although II2PO ( adsorbed by soils has been
replaced by OH- (Dean and Rubins, 1947). Still the mechanism of anion
adsorption and charge reduction is doubtlessly not as simple in soils as
in the case of aluminum hydroxides in solution.
The reduction in charge might itself explain the decrease in "immo-
bilized" water with acid additions since water undoubtedly is attracted
to surfaces by electrical forces of various kinds, including electrostatic
attraction (Michaels, 1959). An equally good argument may be obtained by
resorting to a Structural picture. From that point of view it can be concluded
that the "edge-face" flocculation described by Schofield and Samson (1953)
is destroyed by the addition of large amounts of electrolyte. In this connec-
tion, the sharp break in the liquid limit curves (Fig. 5) for Cecil soil occurs
at the point at which adsorption of anions is complete, as estimated from
conductimetrie titration. The effect of the additional anions seems to be
that of encouraging a degree of dispersion, although the suspensions become
highly viscous. Evidently in this latter condition, either because of some
unique structure or because of its virtual "chargelessness," the clay is
unable to hold as much water as in its natural condition. The interactions
between charge and structure in kaolinitic soils make it almost impossible,
at present, to separate these effects.
Whatever the mechanisms whereby net negative charge is reduced and
anions are adsorbed, the effect of these reactions is drastically to alter the
physical properties of the Cecil soil in contrast to montmorillonitie soils.
Also, the amount and manner in which these properties are altered are a
function of the nature of the anion. Sulfate, tenaciously adsorbed, causes a
greater decrease in liquid limit than chloride, which is weakly adsorbed,
although the difference is not great. With phosphate the reaction is more
complex, as shown by the upswing in the curve, as though one reaction were
 INFLUENCE ON SOME SOIL PHYSICAL PROPERTIES 267

superimposed on another. The s e c o n d a r y a n d t e r t i a r y ionizations of ad-

sorbed H s P O 4 lead to an increase in n e g a t i v e charge (Coleman and Mehlich,
1948) which a p p a r e n t l y enhances t h e r e t e n t i o n of w a t e r b y t h e soil. Phos-
ph at e also has a p r o p e n s i t y to u n i t e w i t h a l u m i n u m an d iron and f o r m
r e l a t i v e l y insoluble c o m p o u n d s in a m a n n e r n o t described for sulfate.

CONCLUSIONS

The scope of this s t u d y does n o t p e r m i t definite conclusions a b o u t t h e

n a t u r e of t h e p h y s i c a l - c h e m i c a l s y s t e m w h i c h obtains in acid, kaolinitic soils
of the southeast. T h e results do e m p h a s iz e t h e effects of different anions
on such soils, in c o n t r a s t to m o n t m o r i l l o n i t e . This m a k e s it a p p a r e n t t h a t
there is d a n g e r in a t t e m p t i n g t o use theories t h a t a p p l y to m o n o v a l e n t
m o n t m o r i l l o n i t e systems t o e x p la in t h e b e h a v i o r of kaolinitic soils. Clearly,
b e h a v i o r predictions based on th e double-layer t h e o r y need r e - e v a l u a t i o n
before a p p h c a t i o n to soils in m u c h of t h e s o u t h e r n region.

REFERENCES

Aylmore, L. A. G. and Quirk, J. P. (1959) Swelling of clay-~ater systems: -Nature, v. 183

pp. 1752-1753.
Bayer, L. D. (1948) Soil Physics: John Wiley and Sons, Inc., New York, 398 pp.
Bolt, G. H. and Warkentin, B. P. (1958) The negative adsorption of anions by clay suspen-
sions: Kollold-Z., v. 156, pp. 41-46.
Casagrande, A. (1932) Research on the Atterberg limits of softs: Public Roads, v. 2, pp. 59-62.
Coleman, N. T. and Mehlich, A. (1948) Some chemical properties of soils as relatec[ to their
cation exchange anion exchange ratios: Soil Sci. Soc. Arner. Proc., v. 13, pp. 175-178.
Dean, L. A. and Rubins, E. J. (1947) Anion exchange in soils, I. Exchangeable phosphorus
and the anion exchange capacity: Soil Sci., v. 63, pp. 377-387.
Falconer, J. G. and Mattson, S. (1933) The laws oI soil colloidal behavior, XIII. Osmotic
imbibition. Soil Sci., v. 36, pp. 317-327.
Lambe, T. W. (1951) Soll Testing ]or Engineers: John Wiley and Sons, Inc., New York,
165 pp.
Lambe, T. W. (1953) The structure of inorganic soil: Proc. ,4met. Soc. Civil Eng., v. 79,
separate no. 315, 49 pp.
Lambe, T. W. (1958) The structure of compacted clay: J. Soil Mech. Found. Div., Proc.
Amer. Soc. Civil Eng., v. 84, pp. 1-3.
Lutz, J. F. and Kemper, W. D. (1959} Intrinsic permeability of clay as affected by clay-
water interaction: Soil Sci., v. 88, pp. 83-90.
Mattson, S. (1927) Anionic and cationic adsorption by soil colloidal materials of varying
SiO~/A1203 + Fe203 ratios: Trans. 1st lnt. Cong. Soil Sci., v. 2, pp. 199-211.
Mehlich, A. (1950) Cation exchange anion exchange ratios of kaolinitic soil colloids: Trans.
4th Int. Cong. Soll Sci., v. 1, pp. 133-135.
Michaels, A. S. (1959) Physico-chemical properties of soils: Soil water systems: J. Soil Mech.
Found. Div., Proc. Amer. Soc. Civil Eng., v. 85, pp. 91-102.
Quirk, J. P. and Theng, B. K. G. {1960) Effect of surface density of charge on the physical
swelling of lithium montmorillonite: Nature, v. 187, pp. 967-968.
18"
268 N I N T ~ NATIONAL CONFERENCE ON CLAYS AND CLAY MINERALS

Rollinson, C. L. (1956) Olation and related chemical processes: in Chemistry of the Coordi.
nation Compounds (edited by Bailer, J. C.): Reinhold Publishing Corporation, New York,
chap. 13, 834 pp.
Schofield, R. K. (1939) The electrical charges on clay particles: Soils and Fert., v. 2, pp. 1-5.
Schofield, R. K. and Samson, H. R. (1953) The deflocculation of kaolinite suspensions and
the accompanying change-over from positive to negative chloride adsorption: Clay Min.
Bull., v. 2, pp. 45-51.
Taylor, A. W. (1959) Physico-chemical properties of soils: Ion exchange phenomena: J. Soil
Mech. Founcl. Div., Proc. Amer. Soc. Civil Eng., v. 85, pp. 19-30.
Thomas, G. W. (1960) Effects of electroly~e imbibition upon cation-exchange behavior of
soils: Soil Sc~. Soc. Amer. Proc., v. 24,.pp. 329-332.
Warkentin, B. P., Bolt, G. H. and l~Ifller, R. D. (1957) Swelling pressure of montmorillonite :
Soil Sci. Soc. Amer. Proc., v. 21, pp. 495-497.
White, W. A. (1955) Water sorption properties of homoionic montmorillonite: in Clays and
Clay Minerals, Natl. Acad. Sei.--Natl. Res. Council, pub. 395, pp. 186-204.