Published January, 1997

Effects of Adsorbed Humic Acid on Surface Charge and Flocculation of Kaolinite

Ruben Kretzschmar,* Dean Hesterberg, and Hans Sticher
ABSTRACT
The behavior of clays in soils, groundwater aquifers, and aquatic
environments is controlled to a large extent by flocculation and disper-
F LOCCULATION-DISPERSION PHENOMENA of clay COl-
loids play an important role in soil structural stability,
suspended sediment behavior in surface waters, colloid
sion phenomena. Dispersed clay particles can become mobile and mobility in soils and groundwater aquifers, as well as
facilitate the translocation of strongly sorbed pollutants in the environ-
industrial applications of clay minerals (van Olphen,
ment. In this study, the adsorption of a soil humic acid to Na-kaolinite
and the resulting effects on surface charge and colloidal stability of
1977; Miller and Baharuddin, 1986; O'Melia, 1989;
kaolinite were investigated in dilute aqueous suspensions. The pH McCarthy and Zachara, 1989; Kretzschmar etal., 1995).
dependence (pH 3-11) of humic acid adsorption to kaolinite in a In soils, clay dispersion can result in surface crusting,
NaClO4 background electrolyte was studied with batch experiments reduced water infiltration, and increased surface runoff
at three different ionic strengths (0.001, 0.01, and 0.1 M). Sorption of and erosion (Miller and Baharuddin, 1986). Clay colloids
humic acid increased with decreasing pH or increasing ionic strength, a that remain suspended in surface runoff or in water
behavior that is typical for anionic polyelectrolytes with carboxylic infiltrating the soil can also enhance the translocation
functional groups. Electrophoretic mobility measurements showed that of adsorbed contaminants, a process that has recently
pure kaolinite had positive net total particle surface charge at low pH attracted much attention (McCarthy and Zachara, 1989).
and negative surface charge at high pH, with an isoelectric point at
pH 4.8 (in 0.01 M NaCIO4). With increasing amounts of humic acid
Numerous studies have been conducted on the floccu-
sorbed to the kaolinite surface, the electrophoretic mobility was contin-
lation-dispersion behavior of soil and reference clays
uously shifted to more negative values. At low pH, this resulted in (AroraandColeman, 1979;GoldbergandGlaubig, 1987;
charge reversal from positive to negative net total particle surface Goldberg and Forster, 1990; Goldberg et al., 1991;
charge. Additions of small amounts of humic acid to the kaolinite Miller et al., 1990; Hesterberg and Page, 1990a;
suspensions resulted in large increases in colloidal stability. At low Kretzschmar et al., 1993). It has been a common observa-
pH, this was probably due to reversal of edge charge from positive' tion that the colloidal stability of soil clays is many times
to negative preventing edge-to-face flocculation. In addition, a general greater than that of comparable reference clays (Goldberg
increase in negative surface charge density and steric stabilization and Forster, 1990; Frenkel et al., 1992; Heil and Sposito,
effects may contribute to the influence of adsorbed humic acid on the 1993a). Also, clays isolated from surface soils were
colloidal stability of kaolinite.
found to be more dispersive than clays from the subsoil
R. Kretzschmar and H. Sticher, Inst. of Terrestrial Ecology, Swiss Federal horizons of kaolinitic soils in the southeastern USA
Inst. of Technology, Grabenstrasse 3, CH-8952 Schlieren, Switzerland; (Miller et al., 1990). Factors that have been suggested
and D. Hesterberg, Dep. of Soil Science, North Carolina State Univ.,
Box 7619, Raleigh, NC 27695. Received 8 Jan. 1996. "Corresponding
author (kretzschmar @ ito. umnw. ethz. ch). Abbreviations: CCC, critical coagulation concentration; DLVO, Derja-
guin-Landau-Verwey-Overbeek; IEP, isoelectric point; OC, organic car-
Published in Soil Sci. Soc. Am. J. 61:101-108 (1997). bon; UV, ultraviolet.
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102 SOIL SCI. SOC. AM. J., VOL. 61, JANUARY-FEBRUARY 1997

to contribute to the dispersibility of soil clays include where v is the particle velocity and E is the electric field
the presence of adsorbed natural organic matter (Miller strength. The electrophoretic mobility is related to the zeta
et al., 1990; Kretzschmar et al., 1993; Heil and Sposito, potential c,, which is the electrical potential at the plane of
1993b), specifically adsorbed anions such as phosphate shear. For clay mineral particles, von Smoluchowski's equation
(Shanmuganathan and Oades, 1983), minor amounts of is most commonly used to convert electrophoretic mobilities
into zeta potentials (van Olphen, 1977; Sposito, 1984):
smectite in kaolinitic clays (Schofield and Samson, 1954;
Arora and Coleman, 1979), and the larger surface u. = e0£><;/T| [4]
roughness of soil clays compared with unweathered refer- where E O is the permittivity of vacuum, D is the dielectric
ence clays (Heil and Sposito, 1995). constant of water, and T| is the coefficient of viscosity. It is
Kretzschmar et al. (1993) studied the colloidal behav- often assumed that the plane of shear is located close to the
ior of clays isolated from three highly weathered, kaolin- inner boundary of the diffuse layer (Hunter, 1981). Therefore,
itic surface soils. They reported that selective removal c, can be regarded as an experimental estimate of VI/D.
of humic substances from the clays by NaOCl treatment Because the plane of shear lies at the inner boundary or
resulted in a strong decrease in colloidal stability. How- slightly within the diffuse layer, Gouy-Chapman theory can
ever, they did not observe significant changes in the be used to calculate the electrokinetic charge density, i.e., the
electrophoretic mobility of the particles. Heil and Sposito charge density at the plane of shear (Hunter, 1981). The
(1993a,b) obtained comparable results for an illitic soil electrokinetic charge density is given by:
clay. These observations led them to speculate that steric
stabilization by adsorbed humic substances may play
an important role (Kretzschmar et al., 1993; Heil and [5]
Sposito, 1993b). In other studies, humic or fulvic acids where sgn(q) equals +1 if c, is positive and — 1 if c, is negative,
were added to reference clay suspensions, which always R is the molar gas constant, T is the absolute temperature, c,
increased colloidal stability (Frenkel et al., 1992; Tar- is the bulk concentration of each charged species in solution,
chitzky et al., 1993). In these studies, however, the Z, is the valence of each charged species, and F is the Faraday
constant. For colloids suspended in a symmetrical electrolyte
adsorption of the added organic matter to the clay and with molar bulk concentration c, the relationship is:
resulting effects on electrophoretic mobility were not
measured and little information was obtained about the sinh(ZFc,/2RT) [6]
mechanisms of stabilization. The objectives of this study Under the assumption that the plane of shear is located close
were to: (i) characterize the adsorption behavior of a to the inner boundary of the diffuse layer, the following relation-
soil humic acid on Na-kaolinite as a function of pH and ship exists between electrokinetic charge density and net total
ionic strength, and (ii) study the resulting effects on particle surface charge density:
surface charge and colloidal stability of kaolinite in dilute
aqueous suspensions. a<; « OP = -OD [7]
Quantitative interpretation of the electrophoretic mobility
THEORETICAL BACKGROUND of clays is difficult, however, for the following reasons: (i)
the exact location of the plane of shear is not known and
The surfaces of colloidal particles in aqueous suspensions are (ii) the von Smoluchowski equation strictly applies only for
almost always electrically charged, resulting in the formation of particles with uniform surface charge density. Clay particles,
an electrical double layer at the solid-water interface. The net however, can have negative charge on the faces and positive
total particle surface charge density (op) can be expressed as charge on the edges, which greatly complicates the structure
the sum of surface charge densities contributed by different of the electrical double layer (Secor and Radke, 1985; Chang
sources of charge (Sposito, 1984): and Sposito, 1994). Nevertheless, electrophoretic mobility
should provide a sensitive parameter to detect changes in net
OP = Co + OH + OK + GOS [1] total particle surface charge density. Because humic substances
where o0 is the permanent charge density due to isomorphic are anionic polyelectrolytes, adsorbed humic acid should con-
substitution in the crystal structure, OH is the pH-dependent tribute negative surface charge according to Eq. [1]. Sorption of
net proton charge density, and ds and o0s are the surface humic acid to kaolinite should therefore shift the electrophoretic
charge densities contributed by ions forming inner-sphere and mobility of the clay particles to more negative values.
outer-sphere surface complexes, respectively. The net total According to the classic DLVO theory of colloidal stability,
particle surface charge density is balanced by the dissociated the interaction energy between two similarly charged colloidal
surface charge density (OD), i.e., the net charge density of particles is determined by the sum of the electrostatic repulsive
dissociated counterions in the diffuse layer: energy and attractive forces arising from van der Waals interac-
tions (Verwey and Overbeek, 1948). Additional repulsive hy-
OP + OD = O [2] dration forces due to adsorbed hydrated ions can also affect
The electrical potential at the plane that separates ions com- the coagulation of particles, especially at high ionic strength
plexed at the surface from dissociated ions in the diffuse (Pashley, 1981). The magnitude of electrostatic repulsive
layer is called the diffuse-layer potential, \|/D. The diffuse-layer forces between two particles is a function of the distance of
potential can be estimated experimentally by electrokinetic separation, the valence and concentration of counterions, and
measurements, such as particle electrophoresis (Hunter, 1981). the net total surface charge density. Thus, sorption of humic
Charged colloidal particles placed in an electric field will move acid to kaolinite may result in increased colloidal stability due to
with a velocity and direction depending on the net total particle increased negative surface charge (electrostatic stabilization).
surface charge density. The electrophoretic mobility is defined Another mechanism by which adsorbed humic substances may
as: increase colloidal stability is steric stabilization caused by a
thermodynamic repulsion that occurs between interpenetrating
U = V/E [3] organic polymer chains attached to the colloid surfaces (Hunter,
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KRETZSCHMAR ET AL.: ADSORBED HUMIC ACID EFFECTS ON KAOLINITE 103

1987). The relative importance of stabilization by electrostatic

and steric interactions for the colloidal stability of clay-humic
complexes is not known, but it seems likely that a combination
of these factors controls stability (electrosteric stabilization).

MATERIALS AND METHODS

Preparation of Kaolinite
The < 1 -|im size fraction of KGa-2 kaolinite from the Source
Clays Repository of the Clay Minerals Society was used in
this study. The KGa-2 kaolinite is a sedimentary kaolinite from
Georgia with a high degree of stacking disorder. Ten-gram
samples of KGa-2 kaolinite were suspended in 200 mL of
deionized water and suspension pH was raised to 9.5 by NaOH
addition. The suspensions were dispersed by sonification and
the <l-nm size fraction was separated by repeated centrifuga-
tion and dispersion steps. The kaolinite obtained was washed
five times with 1 A/NaCl solution and excess salt was removed
by subsequent washings with deionized water. The kaolinite
was redispersed in deionized water, quickly frozen in an ethanol
bath at -35°C, and lyophilized.
The specific surface area of the kaolinite was 23.0 m2 g"1
as measured by multipoint N2-BET analysis. The kaolinite
samples were outgassed for 20 h at 110°C under a constant
N2 stream and then analyzed on a Micromeritics Gemini 2360
surface area analyzer (Micromeritics, Zaventum, Belgium).
X-ray diffraction analysis and visual inspection of the clay by
transmission electron microscopy revealed no trace impurities
of 2:1 type clay minerals or other crystalline phases. The
particles were pseudohexagonal platelets (Fig. 1), which repre-
sents the typical morphology of kaolinites. Fig. 1. Transmission electron micrograph of the <l-um fraction of
KGa-2 kaolinite. Note the typical pseudohexagonal morphology of
the kaolinite platelets. Bar = 0.5 \aa.
Preparation of Humic Acid
Following the procedure of Schnitzer and Schulten (1992), pensions and control humic acid solutions were centrifuged
mimic acid was extracted from a Portsmouth Ap soil sample for 20 min at 6000 x g on a refrigerated centrifuge and the
(sandy skeletal, mixed, thermic Typic Umbraquult) from the supernatants were carefully removed using a pipette. The humic
coastal plain of North Carolina. One-hundred-gram portions acid concentrations remaining in the supernatants were deter-
of air-dry soil were suspended in 1 L of N2-purged 0.5 M mined by UV absorbance at 254 nm. In the concentration
NaOH, shaken for 72 h at 23°C under N2 atmosphere, and range studied, UV absorbance as a function of humic acid
centrifuged. The supernatant solution containing the humic concentration followed Beer's law, resulting in linear standard
and fulvic acid fractions was acidified to pH 1 by adding curves. In some experiments, the absorbance was measured
6 M HC1 to flocculate the humic acid. The ash content of the at three different wavelengths (254, 365, and 465 nm) to check
humic acid was reduced by five subsequent HC1-HF treatments whether certain fractions of the humic acid adsorb preferentially
(Schnitzer, 1982). Further purification and H saturation was on the kaolinite. The UV-VIS absorbance spectra of humic
achieved using precleaned XAD-8 and H-Amberlite resin col- substances are rather featureless but they do depend to some
umns (Malcolm, 1991). Part of the humic acid was freeze- degree on molecular weight and chemical composition (Bloom
dried, and the remainder was stored as a stock solution at and Leenheer, 1989). Preferential adsorption would therefore
4°C. be expected to change the ratios of extinction at different
wavelengths. Unless otherwise noted, reported results are
Adsorption of Humic Acid on Kaolinite based on the UV absorbance at 254 nm, which provided the
greatest sensitivity. The percentage of humic acid sorbed to
Batch experiments were conducted to measure the pH- the clay was calculated as the UV absorbance of each sample
dependent adsorption of humic acid on kaolinite. Stock humic relative to the absorbance of the respective control humic acid
acid solutions were prepared (CO2 free, 1-6 mg OC L""1) in solution, which had the same pH. This was necessary because
0.01 M NaClO4 background electrolyte and 25-mL aliquots the UV absorbance of humic acid is slightly pH dependent.
were pipetted into series of 35-mL polysulfuron centrifuge To assess the effect of ionic strength on humic acid adsorption
tubes. The pH of the solutions was adjusted to values between to kaolinite, similar experiments were conducted at background
3 and 11 by additions of HC1O4 or NaOH (CO2 free, 0.01 M electrolyte concentrations of 0.001 and 0.1 M NaClO4.
or 0.1 M). For each pH level, the centrifuge tubes were
prepared in duplicate. To one of the tubes, a stock kaolinite Electrophoretic Mobility
suspension (20 g L~', same background solution) was added
to give final clay concentrations of 0.2 or 0.4 g L"1, while Electrophoretic mobility measurements at pH values be-
the other tube received the same volume of background solution tween 3 and 11 were used to detect changes in net total particle
and served as a control without clay. The tubes were tightly surface charge density due to adsorbed humic acid. Dilute
capped and equilibrated for 24 h at 25° C on a temperature- kaolinite suspensions (0.2 g L~') were prepared in 0.01 M
controlled reciprocal shaker. After equilibration, the pH values NaClO4 background electrolyte and various amounts of humic
were measured in all suspensions and control solutions using acid were added (0-4 mg OC L~'). Suspension pH was adjusted
a combination glass electrode. For phase separation, the sus- to values between 3 and 11 by addition of NaOH or HC1O4. The
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104 SOIL SCI. SOC. AM. J., VOL. 61, JANUARY-FEBRUARY 1997

suspensions were equilibrated for 24 h under N2 atmosphere and

then electrophoretic mobility and pH were measured simultane- Wave length:
ously at 25°C. The electrophoretic mobility was measured by • 254 nm
electrophoretic light scattering (laser Doppler velocimetry-
D 365 nm
photon correlation spectroscopy) of dilute suspensions placed
in an electric field on a ZetaSizerS (Malvern Instruments, A 465 nm
Malvern, England). The electrode chambers of the AZ4 cell
were filled with background electrolyte without humic acid and
clay. Triplicate measurements were performed in crossed-beam
mode with 30-s count time, 150 V applied voltage, and a
modulator frequency of 1000 Hz.

Colloidal Stability
The stability of the suspensions used for electrophoretic
mobility measurements was evaluated by redispersing them
with an ultrasonic tip and allowing them to flocculate and settle
for 24 h. A 2.5-mL aliquot of the supernatant was then taken 2/400
from a depth of 2 cm and its optical density was determined O 1/200
on a spectrophotometer as the absorbance at 525 nm. The
suspensions were operationally classified as flocculated if ab- D 2/200
sorbance was <0.1 and as stable if absorbance .was X). 1. A 6/400
In addition, GCC values were determined for dilute kaolinite • 4/200
suspensions containing different amounts of humic acid. The
flocculation series test procedure of Hesterberg and Page
(1990b) was used with minor modifications. Series of suspen-
sions (25 mL in 35-mL centrifuge tubes) were prepared con-
taining 200 mg L"' kaolinite, O to 5 mg OC L~' as humic
acid, and increasing electrolyte concentrations between O and
250 mM NaClO4. After dispersing the samples by sonification,
they were allowed to flocculate for 24 h at 25 ± 1.0°C. A
2.5-mL aliquot of the supernatant solution was removed from Background electrolyte:
each tube from a depth of 2 cm and its optical density was A 0.100MNaCIO4
determined at a wavelength of 525 nm. The GCC was operation- 0.010MNaCIO4
ally defined as the electrolyte concentration required to reduce n 0.001 M NaClOx
the optical density of the supernatant solution to 20% of the
initial value. At the end of the flocculation period, the pH
measured in all suspensions using a combination glass electrode
was pH 5.5 ± 0.3.

RESULTS AND DISCUSSION

Adsorption of Humic Acid
6 10
A typical example for the pH-dependent adsorption
of humic acid on Na-kaolinite is shown in Fig. 2A. SUSPENSION pH
In this experiment, the concentrations of humic acid Fig. 2. Adsorption of the Portsmouth soil humic acid to Na-kaolinite
remaining in solution were determined spectrophotomet- as a function of pH and ionic strength (I): (A) adsorption envelope
rically at three different wavelengths. All three wave- experiment in which the humic acid concentration in solution was
measured spectrophotometrically at three different wavelengths
lengths gave practically identical results, indicating that (/ = 0.01 M, 400 mg clay L"1, 6 mg OC L'1); (B) adsorption
preferential adsorption of certain fractions of the humic envelopes (/ = 0.01 M) with varying concentrations of kaolinite
acid was insignificant and UV absorbance was a good (in milligrams clay per liter) and humic acid (in milligrams OC
measure for the humic acid concentration remaining in per liter); and (C) adsorption envelopes at three different ionic
strengths (200 mg clay LT1, 4 mg OC L"1).
solution. This is in agreement with a study by Murphy et
al. (1990) in which the possible fractionation of Suwannee
humic acid during adsorption on hematite was tested. acid to Na-kaolinite generally decreased with increasing
They conducted four sequential sorption experiments pH. The strongest decrease in humic acid adsorption
to compare the sorption behavior of the dissolved OC occurred between pH 3 and 7, while above pH 7, the
remaining in the supernatants with the sorption behavior pH dependence was less pronounced. The amounts of
of the total Suwannee humic acid. They found no evi- humic acid sorbed at different fixed pH values were
dence for fractionation of Suwannee humic acid during obtained by interpolation using the cubic spline fits and
adsorption on hematite. adsorption isotherms were constructed from these data.
A set of adsorption envelopes at a background electro- Such isotherms, fitted with the Langmuir isotherm equa-
lyte concentration of 0.01 M NaClO4 for suspensions tion, are shown in Fig. 3A. The Langmuir equation is
containing different amounts of kaolinite and humic acid written as
are depicted in Fig. 2B. The lines represent cubic spline
fits to the experimental data. The adsorption of humic S = KCbl(\ + KC) [8]
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KRETZSCHMAR ET AL.: ADSORBED HUMIC ACID EFFECTS ON KAOLINITE 105

drated cations on the surface, and hydrophobic adsorption

of uncharged parts of humic acid macromolecules (Mur-
phy and Zachara, 1995). The pH and ionic strength
dependence of humic acid adsorption on Na-kaolinite is
most likely due to a combination of several mechanisms:
(i) increased specific adsorption of humic acid on edge
surfaces of kaolinite at low pH, (ii) increased electrostatic
attraction between humic acid and positively charged
edge surfaces of kaolinite at low pH, (iii) increased
sorption of humic acid by cation bridging in the presence
of higher concentrations of Na + , and (iv) changes in the
macromolecular configuration of humic acid as a function
of pH and ionic strength. Specific adsorption via ligand
exchange is believed to be the dominant mechanism for
humic acid binding on oxide surfaces and edges of clay
minerals, especially at low pH (Parfitt et al., 1977;
Gu et al., 1994; Murphy and Zachara, 1995). Specific
adsorption of organic ligands via ligand exchange re-
quires protonated surface hydroxyl groups and therefore
increases with decreasing pH. The effect of macromolec-
ular configuration of humic acid can be envisioned as
follows. At high ionic strength, the negative charges
on humic acid macromolecules are well screened and
consequently the humic acid molecules wind up like
random coils (Ghosh and Schnitzer, 1980). In this con-
figuration more humic acid can be adsorbed to the surface
at monolayer coverage resulting in higher sorption max-
6 ima (Murphy et al., 1994). With decreasing ionic
strength, the thickness of the electric double layers
C (mg C L1) around negatively charged functional groups on the hu-
Fig. 3. Adsorption isotherms for Portsmouth soil humic acid on Na- mic acid macromolecules increases and consequently the
kaolinite at constant pH values (/ = 0.01 A/): (A) isotherms fitted molecules spread out as flexible, linear or branched
with a Langmuir equation, and (B) corresponding linearized Lang-
muir plots. In both plots C is the equilibrium concentration of polymer molecules (Ghosh and Schnitzer, 1980). In this
humic acid in solution and S is the amount of humic acid sorbed configuration the molecules occupy more space on the
to the clay. surface, resulting in lower adsorption maxima (Murphy
et al., 1994). The macromolecular configuration of humic
where S is the amount of humic acid sorbed, C is the acid also strongly depends on pH. With decreasing pH,
equilibrium humic acid concentration in solution, b is the the acid functional groups become increasingly proton-
adsorption maximum, and K is a dimensionless parameter ated and the macromolecular configuration changes from
related to the binding strength. The corresponding linear- the flexible polymer to the random coil type configuration
ized Langmuir isotherms are plotted in Fig. 3B. The (Ghosh and Schnitzer, 1980). Therefore, the pH depen-
sorption data were2 well described by the Langmuir iso- dence of humic acid adsorption on Na-kaolinite may
therm equation (r > 0.988). The sorption maximum also be partially due to changes in the macromolecular
(b) and binding strength (K) increased with decreasing configuration of humic acid.
suspension pH. The sorption maxima were almost
reached at solution humic acid concentrations of 1 to Electrophoretic Mobility
2 mg OC L"1. As shown by the adsorption envelopes
in Fig. 2C, adsorption of humic acid to Na-kaolinite The results of electrophoretic mobility measurements
also increased with increasing ionic strength. From the for kaolinite in the absence and presence of various
data shown, the greatest increase in humic acid adsorption amounts of humic acid are shown in Fig. 4. The electro-
occurred between 0.01 and 0.1 M NaClO4. phoretic mobility of pure kaolinite was strongly pH de-
Similar pH and ionic strength dependent adsorption pendent. At low pH, kaolinite exhibited positive electro-
behavior was previously observed for humic and fulvic phoretic mobility, indicating that the particles carried
acid on goethite, gibbsite, and imogolite (Parfitt et al., positive net total particle surface charge. With increasing
1977), humic substances on goethite (Tipping, 1981), pH, the electrophoretic mobility decreased from positive
natural organic matter and fulvic acid on goethite (Day to negative values, going through an IHP near pH 4.8. At
et al., 1994) and hematite (Gu et al., 1994), and humic high pH, the kaolinite was strongly negatively charged.
acid on kaolinite (Murphy et al., 1990, 1994). Organic These results are in good agreement with data published
compounds such as humic and fulvic acids can adsorb by Anderson and Bertsch (1993) for KGa-2 kaolinite.
to mineral surfaces by a variety of mechanisms including The electrokinetic behavior of kaolinite is a result of a
electrostatic attractive forces, specific adsorption via li- combination of pH-dependent charge on the edge surfaces
gand exchange with protonated surface hydroxyl groups, and small amounts of permanent negative charge on
cation bridging, water bridging in the presence of hy- the basal surfaces. At low pH, the edges are strongly
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106 SOIL SCI. SOC. AM. J., VOL. 61, JANUARY-FEBRUARY 1997

positively charged, resulting in positive net total particle Colloidal Stability

charge. With increasing pH, the edge sites become in- The colloidal stability of the suspensions used for
creasingly deprotonated. At the IEP, the positive charge electrophoretic mobility measurements is illustrated in
on the edges is balanced by the negative permanent Fig. 6. The data shown are optical density measurements
charge on the faces, resulting in zero electrophoretic of the supernatants after a flocculation period of 24 h.
mobility. As the pH increases above pH 5 to 7, the edge For each humic acid level, a sharp cutoff pH value
sites also become negatively charged. (critical pH) was observed separating stable and floccu-
The presence of small concentrations of humic acid lated systems. Above the critical pH, the suspensions
resulted in charge reversal at low pH and an increased remained stable, whereas at lower pH values the particles
negative net total particle charge at pH > IEP (Fig. 4). flocculated and settled within 24 h. The critical pH values
The effect of humic acid addition on the electrophoretic and the corresponding electrophoretic mobilities and zeta
mobility of kaolinite was greatest at low pH. The humic potentials for kaolinite suspensions containing different
acid is more negatively charged at high pH, but it was amounts of humic acid are summarized hi Table 1.
adsorbed much less to the kaolinite compared with With increasing humic acid concentration, the critical
low-pH conditions (Fig. 2). pH dropped from pH 10.7 to <3.0. The electrophoretic
By combining the electrophoretic mobility (Fig. 4) mobility at the critical pH increased from -3.4 to above
and adsorption (Fig. 3) data, we can plot electrophoretic -2.7 (10~8 m2 s"1 V"1), indicating that steric stabiliza-
mobility or zeta potential as a function of the total amount tion may contribute to the stability of kaolinite suspen-
of humic acid in suspension (Fig. 5A), the equilibrium sions in the presence of adsorbed humic acid, in addition
humic acid concentration in solution (Fig. 5B), or the to electrostatic stabilization. However, adsorbed humic
amount of humic acid adsorbed to the kaolinite (Fig.
5C). It is evident that small additions of humic acid (0.5
mg OC LT1) resulted in strong effects on the electropho-
retic mobility of Na-kaolinite. Increasing the humic acid
concentration above 1 to 2 mg OC L"1 had no further s
effects on humic acid sorption (Fig. 3A) or electropho- z
retic mobility (Fig. 5A) of the clay. The adsorption and o
o-
electrophoretic mobility data are consistent, since only
the adsorbed humic acid is expected to affect electropho- ­ ­60
retic mobility and surface charge density. Plotting elec-
trophoretic mobility or zeta potential as a function of 1 2 3 4 5
the amount of humic acid adsorbed (Fig. 5C) shows that HUMIC ACID TOTAL (mg OC L1)
the electrophoretic mobility was continuously shifted to
more negative values with increasing amounts of humic
acid adsorbed. Similar relationships can be obtained for
electrophoretic charge density (Eq. [5]) as a function of
adsorbed humic acid.

D Pure kaolinite _
• 0.5 mg OC L1
A 1.0 mg OC L"'
• 2.0 mg OC L1
0 2 4 6
HUMIC ACID IN SOLUTION (mg OC L1)
«!
OQ
O • •
­ pH 4
A­A pH5 >
O
Q. • ­• pH 6
T­T pH 8 <
OC K
O N »­» pH 10 Z
HI

O
DC
5
CL

a i*
LU
N

12

HUMIC ACID ADSORBED (mg OC g'')

SUSPENSION pH
Fig. 5. Influence of humic acid on electrophoretic mobility (EM) and
Fig. 4. Electrophoretic mobility and calculated zeta potential of pure zeta potential of kaolinite at constant pH values (/ = 0.01 A/).
kaolinite and kaolinite in the presence of various amounts of humic Mobility and zeta potential are plotted (A) as a function of the
acid (200 mg clay L~', 0.5-4.0 mg OC L- 1 ). Electrophoretic mobil- total concentration of humic acid, (B) as a function of the humic
ity was converted to zeta potential using von Smoluchowski's equa- acid concentration in solution, and (C) as a function of the amount
tion (Eq. [4]). of humic acid sorbed to the clay.
 14350661, 1997, 1, Downloaded from [Link] by University Of Aberdeen The Uni, Wiley Online Library on [28/09/2024]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
KRETZSCHMAR ET AL.: ADSORBED HUMIC ACID EFFECTS ON KAOLINITE 107

acid may shift the plane of shear away from the mineral Table 1. Critical pH values and corresponding electrophoretic
mobilities (EM) and zeta potentials of kaolinite suspended in
surface, which could also provide an explanation for this 0.01 M NaCIO4 electrolyte solution containing various amounts
effect. of humic acid. At pH values below the critical pH, the suspen-
The results of flocculation series tests with kaolinite sions flocculated within 24 h, whereas above the critical pH
suspensions containing different total amounts of humic they remained stable.
acid are presented in Fig. 7A. The resulting GCC values Humic acid Critical pH EM Zeta potential
as a function of total humic acid concentration are shown mg OC L~' 10-» m2 s-' V-' mV
in Fig. 7B. Here, the GCC value was denned as the 0.0 10.7 -3.4 -43
electrolyte concentration at which the optical density of 0.5 5.9 -3.4 -43
the supernatant solution was reduced to 20% of the initial 1.0 4.6 -3.0 -38
2.0 3.2 -2.7 -34
value. Pure kaolinite flocculated even in deionized water 4.0 <3.0 -2.7 -34
at pH 5.5. With increasing humic acid concentration,
the GCC values continuously increased (Fig. 7B). useful for understanding the relationships between ad-
At low humic acid concentrations, sharp cutoffs be- sorbed humic acid, surface charge, and colloidal stability
tween dispersed and flocculated systems were observed of kaolinite.
(Fig. 7A). With increasing humic acid concentration,
however, the optical density vs. ionic strength curves
flattened out and a sharp cutoff was not observed. This CONCLUSIONS
may be explained by the ionic strength dependence of. Adsorption of humic acid to Na-kaolinite strongly
humic acid adsorption on kaolinite. Within each floccula- increased with decreasing pH or increasing ionic
tion series test, the amount of humic acid adsorbed to the strength. The adsorption isotherms for humic acid on
clay increases with increasing electrolyte concentration kaolinite in dilute suspensions were of the high-affinity
even though the total humic acid concentration remains type and were well described by a Langmuir equation.
constant. Because the adsorbed humic acid stabilizes the
clay, the sharp cutoff between dispersed and flocculated
systems is not observed in the presence of higher concen-
0.4 mg OC L'1
trations of humic acid. The interpretation of GCC values 0.5 mg OC L'
of clays in the presence of different amounts of humic 1.0 mg OC L1
acid, as also previously published by other researchers 2.0 mg OC L '

(Frenkel et al., 1992; Tarchitzky et al., 1993), is there- o 3.0 mg OC L '

4.0 mg OC L'
fore not straightforward. Direct measurements of the 1 5.0 mg OC L '
DC
flocculation kinetics at fixed pH and ionic strength but
varying amounts of adsorbed humic acid may be more S

" " Pure Kaolinite

0.4 ~

0.2 O 50 100 150 200 250 300

:
0
/ NaCIO4 (mM)
103
"Fc ­ B
B
0.4
in
<M
.
* . •. • ••.­ •. , ­ .•
LO,
0.2
/ 0.5 mg OC L1 102
LU /
Cl 0 U——> • • W i——i——i——.——i——J
ORBAN!

A A
C A .A . A AA O
0.4 /A A" A " A A
CO : / 8
m 0.2 / 1.0 mg OGL1
<
10°
n ^ . 1 . I . .
­D
04 .^­^­^%% . ­ • • 10'1
10'1 10° 101
0.2
" / 2.0 mg OC L1
• , . i . i . i .
HUMIC ACID (mg OC L')
n
6 8 10 Fig. 7. Results of flocculation series tests for kaolinite at pH 5.5 ±
SUSPENSION pH 0.3 in the presence of various amounts of humic acid: (A) relative
absorbance (at 525 nm) of supernatants after a flocculation period
Fig. 6. Absorbance (at 525 nm) of the supernatants after a 24-h of 24 h, and (B) resulting critical coagulation concentrations (CCC)
flocculation period. Suspensions were classified as flocculated if in NaClO4 electrolyte as a function of the total humic acid concentra-
absorbance was <0.1. Note the sharp pH cutoff (critical pH) separat- tion. The CCC was defined as the electrolyte concentration necessary
ing stable and flocculated systems. to reduce the optical density of the supernatants to 20%.
 14350661, 1997, 1, Downloaded from [Link] by University Of Aberdeen The Uni, Wiley Online Library on [28/09/2024]. See the Terms and Conditions ([Link] on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
108 SOIL SCI. SOC. AM. J., VOL. 61, JANUARY-FEBRUARY 1997

The adsorption behavior of humic acid is typical for

anionic polyelectrolytes with carboxylic functional
groups and can be explained by a combination of several
factors, including specific adsorption to edge surfaces
of kaolinite and conformational changes of humic acid
macromolecules as a function of pH and ionic strength.
Small amounts of adsorbed humic acid strongly affected
the surface charge and electrophoretic mobility of the
kaolinite particles. At low pH, <1 g kg"1 of adsorbed
OC was necessary to cause reversal of the net total
particle surface charge from positive to negative. Small
amounts of adsorbed humic acid also strongly increased
colloidal stability. The effects of adsorbed humic acid
on colloidal stability appear to result from a combination
of electrostatic and steric stabilization; however, it is
difficult to resolve the relative importance of both mecha-
nisms. At low ionic strength, electrostatic stabilization
and prevention of edge-to-face flocculation is probably
most important. With increasing amounts of adsorbed
humic acid at high ionic strength and/or low pH, steric
stabilization may become increasingly effective.

ACKNOWLEDGMENTS
We thank Daniel Grolimund for critically reviewing an
earlier draft of this paper and Dr. Ernst Wehrli (Laboratory
for Electron Microscopy, ETH Zurich) for his support with
transmission electron microscopy. This research was funded
by ETH Zurich and Project NC05758 of the North Carolina
Agricultural Research Service.