You are on page 1of 4

Aust. J. Soil Res.

, 1974, 12, 173-6


Short Communication

The Influence of Net Charge


on Water Dispersible Clay and Sorbed Snlphate

G. P. Gillman
Division of Soils, CSIRO, Pastoral Research Laboratory, Townsville, Qld 4810.

Abstract
The variation of net electric charge with pH at four electrolyte concentrations has been determined on
samples from four horizons of a krasnozem soil in north Queensland. A potentiometric titration
technique was employed, which allowed the estimation of the zero point of charge (zpc) for each
sample. Variation in zpc was related to organic matter content and clay mineralogical composition.
The charge distribution characteristics explain the amounts of water dispersible clay and phosphate
extractable sulphate in this soil.

The phenomenon of water dispersible clay (WDC)has been studied by Isbell et al.
(unpublished data) in the red basaltic soils (krasnozems and euchrozems) of north
Queensland. The soil was agitated in demineralized water overnight in a reciprocating
shaker, the suspension was placed in a sedimentation cylinder, and the amount of
clay dispersed determined by a pipette method. It was found that there is nearly
always 20-40 % WDC in the upper 20 or 30 cm (sometimes to 60 cm) of the profile,
and usually little or no WDC below this depth, although there are exceptions as in the
case of the profile discussed here. Also in some profiles, WDC is present in all
horizons. Probert (personal communication) has found that native sorbed sulphate
(extractable with dilute calcium phosphate; Barrow 1967) increases with depth in the
krasnozem soils. Such an increase is not accompanied by a decrease in soil pH
(Gillman, unpublished data). It was felt that these properties could be explained in
terms of the net electric charges on the soil particle surfaces.
Samples from four depths of a krasnozem profile, under virgin rain-forest from
Gregory Falls (Innisfail 1 : 250,000 385786), were used for serial titrations following
the procedure of van Raij and Peech (1972). This profile was of interest because of
its water dispersible clay characteristics (Fig. 1). The potentiometric titration curves
of net charge versus pH at four salt concentrations are illustrated in Fig. 2.
These curves clearly have a common point of intersection, showing that the
electric charge on the soil particle surface can be reversed. The system, therefore, is
of the type described by van Olphen (1963) as one having a constant surface potential.
For such a system, the difference between the pH measured in water and that
measured in IN potassium chloride should indicate the sign of the net charge (Mekaru
and Uehara 1972; van Raij and Peech 1972). If pHlN - pH,,, (ApH) is ,,
positive, the net charge is positive and vice versa. From Table 1 it is seen that when
ApH becomes small, i.e, when the soil is near its zero point of charge (zpc), WDC
becomes small. The presence of a net charge, whether negative or positive, produces
Short Communication

repulsive forces which are sufficiently strong (particularly in low electrolyte con-
centrations) to overcome forces of attraction arising from van der Waal forces, or
from attraction between opposite charges on particle surfaces, so that some clay
remains dispersed.

Table 1. Data for a krasnozem profile from Gregory Falls, north Queensland
Sign Phosphate
Depth of Soil extractable Total Organic Clay mineralogyE
(cm) WDC A~HA net pHB sulphate clay matter
charge (ppmIC (%) (%) K Go G H

0- 10 33.7 -0.90 - 5.6 34 60 11.5 n.d.


10- 20 32.8 -0.92 - 5.7 69 80 6.8 10-20 40-50 20-30 5-10
20- 30 13.8 -0.39 - 5.4 58 86 4.6 n.d.
30- 60 0.1 -0.10 - 5.5 240 78 3.1 20-30 40-50 30-40
60- 90 <O 1 -0.04 5.4 320 2.0 n.d.
90-120
210-240
0.1
49 2
+0.15
TO 50
-
-

+
5.4
5.3
370
1630
n.d.
75
65
1.3
20-30
n.d.
40-50 30-40
450-510 <0.1 -0.12 - 5.1 1200 60 n.d. >80 5-10F 5-10
A See text. B pH in 1 : 5 soil : water at 25'C. C Method of Barrow (1967); Probert, unpublished data.
D n.d., not determined. E K, kaolin; Go, goethite; G , gibbsite; H, hematite. F Unable to
distinguish hematitelgoethite.
WDC (%)

Fig. 1. Water dispersible clay


content versus depth
for a krasnozem profile.

The pH differences shown in Table 1 indicate that the zpc is approaching higher
pH values as the depth increases to the 210-240 cm horizon. Since the clay mineral-
ogical composition does not vary over this depth (Table I), the effect may be due to
Short Communication

the decrease in organic matter content (van Raij and Peech 1972). It is postulated that
negatively charged organic matter is held at positive sites on the mineral surfaces, and
that a decrease of organic matter content with depth is accompanied by exposure of
increasing numbers of positive sites which are responsible for the observed changes in
sulphate sorption. In the 450-510 cm horizon, the clay mineralogy has changed to a
system dominated by kaolinite. The zpc is lower than that of the 210-240 cm
horizon, the amount of positive charge has been reduced, and consequently, the
sorbed sulphate value is decreased. The actual amount of sorbed sulphate is high,
indicating that a good deal of positive charge is present, but the increased amount of
negative charge from the kaolinite causes the net charge to be low. (Hence, also, the
absence of WDC.) Barrow et al. (1969) showed that native sorbed sulphate was
positively correlated with rainfall on a range of soils derived from a variety of parent
materials. The explanation could be that rainfall is correlated with leaching and
hence with the intense weathering that produces positive charges.

Fig. 2. Net electric charge as determined by potentiometric titration, o I N sodium


chloride; 0. IN sodium chloride; A 0 . 0 1 sodium
~ chloride; x 0 , 0 0 2 ~
sodium chloride.
(a) 10-20 cm, zpc 4.5; (b) 90-120 cm, zpc 5.4; (c) 210-240 cm, zpc 5.8; (d) 450-510 cm,
ZPC 5.2.

The position of the zpc in the upper horizons is lower than would be expected
from the dominant oxides which have isoelectric points above pH 7. The samples
studied by van Raij and Peech (1972) had even lower zpc values. It is possible that
the hydrochloric acid pretreatment given to the soil did not remove sorbed sulphate,
the presence of which would lower the zpc (Hingston et al. 1972).
Van Raij and Peech (1972) have clearly illustrated the influence of pH and electro-
lyte concentration on the cation exchange properties of soils with completely revers-
ible interfaces. The charge distribution characteristics have been used here to explain
Short Communication

such different properties as water dispersible clay content and sulphate sorption. The
author concludes that the zero point of charge, particularly in kaolinitic or
sesquioxidic soils, is a fundamental soil property, and further work, aimed at
developing less tedious methods for determining zpc and the distribution of charge
with pH and ionic strength, as well as establishing the general applicability of the
above observations, is in progress.

References
Barrow, N. J. (1967). Studies on extraction and on availability to plants of adsorbed plus soluble
sulphate. Soil Sci. 104,242-9.
Barrow, N. J., Spencer, K., and McArthur, W. M. (1969). Effects of rainfall and parent material
on the ability of soils to adsorb sulphate. Soil Sci. 108, 120-6.
Hingston, F. J., Posner, A. M., and Quirk, J. P. (1972). Anion adsorption by goethite and gibbsite. I.
The role of the proton in determining adsorption envelopes. J. Soil Sci. 23, 177-92.
Mekaru, T., and Uehara, G. (1972). Anion adsorption in ferruginous tropical soils. Pvoc. Soil Sci.
Soc. Am. 36,296-300.
van Olphen, H. (1963). 'Introduction to Clay Colloid Chemistry.' (Interscience: New York.)
van Raij, B., and Peech, M. (1972). Electrochemical properties of some oxisols and alfisols of the
tropics. Pvoc. Soil Sci. Soc. Am. 36, 587-93.

Manuscript received 14 February 1974

You might also like