PhD

A study has been conducted in seven selected profiles of Oxisols and
Ultisols representing the important pedological units with a wide geographical
distribution in the state to have a deeper insight in to the electro-chemical
behaviour of these soils. A multipronged approach to the studies made are
highlighted to enable a clear understanding of the achievements as against the
major objectives and approaches made.
A
laboratory study with thirty six samples from seven profiles
representing six Ultisols and one Oxisol has been carried out. Path coefficient
analysis of important thirteen charge contributing factors against two
parameters for measurement of charge and the inter-relationship of 15 soil
characters show that organic matter5, clay %, R2 O3%, Alo% and Feo% are
the major factors that control the surface charge behaviour of the soils. The
factors studied explained only 55% and 48% of the variability of cation
exchange and anion exchange respectively.
Study of the distribution of the electric charges in the surface and sub-
surface horizons of the soils was made by the means of potentiometric
titrations and by measurement of adsorption of ions
in the presence of
varying concentration of electrolytes. The titration curves at different ionic
strengths crossed at the common point intersection the zero-point of charge
(zpc). Thus the electro-chemical behaviour of these soils was found to be
similar to that exhibited by many metallic oxides in which the surface
potential of reversible double layer is determined solely by the activity of
potential determining ions, H+ and OH- in the bulk of the solution. The zpc
for the surface horizons was found to be lower than the sub-surface and sub-
surface horizons in all the soils studied. Soil to soil variation in zcp between
surface and sub-surface horizons were more or less the same for all samples.
Thus zcp can not be recommended as a taxonomic tool in soil classification to
distinguish Oxisols from Ultisols.
From known values of surface area and zpc of these soils, the values
for net electric charge was calculated by the application of the Gouy-
Chapman model of double layer and was found to obey the theory only at a
critical electrolyte concentration. As the soils were found to be similar to that
of constant potential systems, the charge distribution varied substan\tially
with PH and electrolyte concentration. Direct measurement of adsorption of
ions from solutions of KC1 NaCl and CaCl2 showed that the nature and
valence of index cations also influenced the magnitude of the negative charges
on the soils particles.
On the basis of the influence of PHJ, electrolyte
concentration and the valence of the counter-ions on the electric charges of
the soils most of the conventional methods of ion-exchanged determinations
using buffered electrolytes at high concentrations appears to be inappropriate
for tropical soils.
In a study for the evaluation of ion-exchange measurements it was
found that the compulsive exchange methods is most suitable for the
combined estimation of CEC and AEC. The traditional ammonium acetate
method was found to give over estimations of CEC and thus very high values.
Calcium chloride, 0.002 M was found to be equally effective but owing to the
simplicity of the procedure, the former appeared better. The compulsive
exchange method is free from the inherent defects of neutral normal
ammonium acetate and hence would seem well suited for the Oxisols and
Ultisols of Kerala.
Although sesquioxidic components in combination with organic
matter apparently dominate the charge properties of these soils, there was
evidence from the titration curves to shows the presence of small amounts of
clay minerals with permanent negative charge.
This was confirmed by
different methods and was found in good agreement with the estimated
theoretical results. However under field conditions the expression of this
constituent was minimum and the variable charge components such as Fe, al
oxides certainly control the electro-chemical characteristics.
In a separate experiment to find out the contribution of organic
matter and sesquioxides towards exchanges properties of soils, it was
observed that bout 64% of the negative sites and 8% of the positive was
contributed from organic matter. Sesquioxides explained only 11% of the
variablility in CECX and 22% of the variability in AEC. The combined effect
of organic matter and R2O3 removal was highly significant with respect to
CEC and AEC in all the soils studied.
Mineralogical investigation revealed the presence of kaolinite as the
dominant clay mineral.
Appreciable amounts of smectities, quartz and
gibbsite was also identified.
The presence of smectities was not reflected in
the CEC of any of the samples. Scanning electron micrographs did not give
much information other than the presence of a thick coating of iron and
amorphous materials over clay aggregates. The specific surface measured by
ethylence glycol retention method invariably showed higher values than the
determined values obtained for negative adsorption data. The specific surface
determined closely followed the organic matter content of the samples inspite
of the vertical increase in clay content with in profiles.