Journal of Colloid and Interface Science 218, 225–232 (1999)
Article ID jcis.1999.6419, available online at http://www.idealibrary.com on
Adsorption/Desorption in a System Consisting of Humic Acid,
Heavy Metals, and Clay Minerals
Aiguo Liu and Richard D. Gonzalez 1
Chemical Engineering Department, Tulane University, New Orleans, Louisiana 70118
Received February 8, 1999; accepted July 12, 1999
Metal adsorption/desorption in a system consisting of humic
acid, metal ions, and clay minerals is described. Montmorillonite
and purified humic acid were selected as a prototype materials for
this study. At a constant ionic strength, the amount of humic acid
adsorbed on montmorillonite decreases when pH is increased. A
slight increase in humic acid adsorption on montmorillonite is
observed when there are bivalent metals present in the system. The
metal adsorption on montmorillonite does not correlate to the
amount of humic acid adsorbed on montmorillonite. Montmoril-
lonite with preadsorbed humic acid does not show a significant
change in the capacity of adsorbed metal ions. An increase in the
ionic strength at a pH of 6.5 results in an increase in the adsorption
of lead on montmotillonite in the presence of humic acid, while at
a lower pH, the increase in ionic strength results in a decrease in
metal adsorption. The bridging of bivalent metal ions between
montmorillonite and humic acid is proposed as the dominant
adsorption mechanism. © 1999 Academic Press
Key Words: adsorption/desorption; humic acid; montmorillon-
ite; heavy metals.
INTRODUCTION
The adsorption of heavy metals by sediments and natural
organic materials (NOM) is an important mechanism that con-
trols metal concentration in aqueous systems. Montmorillonite
together with kaolinite and quartz are the primary constituents
of sediments found in the lower Mississippi Delta (G. C.
Flowers, personal communication, 1995). The substitution of
Al 31 for Si 41 in the tetrahedral sheet and Mg 21 for Al 31 in the
octahedral sheet induces a negative charge on montmorillonite
(1). Typical montmorillonites, such as Wyoming montmoril-
lonite, have a cation exchange capacity (CEC) around 80
meq/100g and a point of zero charge (PZC) of approximately
2.5 (2). Under general environmental conditions, its surface is
always negatively charged. Humic substances are present in
aqueous systems and can exist either in solution or as a
precipitate mixed with sediments. They tend to associate into
complex chemical structures that are more stable than the
starting materials (3, 4). About 80% of the dissolved organic
1
To whom correspondence should be addressed. Fax: 504-8656744. E-mail:
gonzo@tsc.tulane.edu.
225
materials (DOM) consist of humic substances. In natural water,
about 50% of the DOM consists of humic and fulvic acids (5).
The ecotoxicology of heavy metals is determined by the path-
way of decontamination in a natural aqueous system. Humic
substances provide important sources of dissolved adsorbent
organic ligands and, therefore, are expected to influence the
bioavailibility and mobility of metals in soil, sediments, and
aquatic systems. With respect to the potential toxicity of heavy
metals, adsorption by humic substances is believed to reduce
metal uptake by organisms.
Extensive studies have been carried out on the adsorption of
metals on sediments. Most of the laboratory studies performed
in the last two decades have been focused on the adsorption of
heavy metals on well-characterized particulates, especially the
oxides (6 –13). Experimental studies of metal adsorption on
various clay materials have been widely carried out.
Humic acid and fulvic acid adsorb on the surface of particles
and may alter their surface properties. They may also complex
with the metal ions changing the interaction between the metal
ions and solid particles. Numerous studies have shown the
presence of a strong interaction between humic substances and
clay minerals even though both are negatively charged under
normal pH conditions (14 –17). Zhou et al. (12) found that the
humic substance uptake by montmorillonite increases with
ionic strength. The reasons for this increase in humic acid
uptake were assumed to be the neutralization of surface
charges and the compression of diffuse double layers. The
latter was believed to be more important.
Taylor and Theng (18) found that the sorption of cadmium
by kaolinite increased with an increase in the humic acid
concentration and solution pH. Maguire et al. (19), on the other
hand, found that the addition of humic acid to the clay–Cs
system depressed the sorption of Cs by clays and enhanced the
desorption of Cs. The phenolic and carboxylic groups (-OH
and -COOH) are believed to be the most active adsorption sites
on humic and fulvic acid. Lövgren and Sjöberg (20) studied
Cu, Ca, and Hg complexation with NOM concentrated from
bog-water at 0.1 M ionic strength. Kerndorff and Schnitzer
(21) investigated sorption of various metal ions on humic acid
at different pH, metal concentration, and HA concentration and
found that the order of sorption efficiency is a function of pH.
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226 LIU AND GONZALEZ
For example, at pH 2.4, the sorption efficiency order is Hg .
Fe . Pb . Cu 5 Al . Ni . Cr 5 Zn 5 Cd 5 Co 5 Mn, but
at pH 5.8, the order is Hg 5 Fe 5 Pb 5 Al 5 Cr 5 Cu . Cd .
Zn . Ni . Co . Mn. Hg(II) was the most easily adsorbed
metal by HA, and Mn was the most difficult. Ca inhibits the
adsorption of trace metals on HA more effectively than Mg
(22).
Electrochemical methods have been widely used to study
metal adsorption on humic acid and fulvic acid. These methods
include such techniques as ion-selective electrodes (ISE) and
anodic stripping voltammetry (ASV) (22–26). The advantage
of electrochemical methods of analysis is that one can make in
situ measurements without the need to separate the complexed
ions from the free metal ions. A major drawback of ISE, from
our own experience, is that a steady reading is not easy to
obtain. This may be due to the adsorption of humic acid or
fulvic acid molecules on the surface of the electrodes. As for
the ASV, the detection limit is not low enough to meet the
usual conditions of metal concentration.
Malcolm and MacCarthy (27) concluded that commercial
humic acids are not representative of aquatic or soil humic
acids. Following a comparison using calcium titration data for
Aldrich and Suwannee Stream humic acids, Hering and Morel
(28) concluded that the use of reprecipitated commercial humic
acid in preliminary studies of metal complexation is adequate
to within a first approximation.
The purpose of this study is to obtain a better understanding
of how humic substances influence metal adsorption/desorp-
tion under different environmental conditions. Montmorillonite
and humic acid are selected as prototypes in this study. Em-
phasis is placed on the system of humic acid–metal ions and
montmorillonite.
EXPERIMENT
Materials and Supplies
The sodium form of montmorillonite from Crook County,
Wyoming, was supplied by the Source Clay Minerals Repos-
itory, University of Missouri, Columbia. After pretreatment
with 0.1 M HCl and 0.5 M NaCl (29), the solution was allowed
to settle. The larger particles which precipitated from the wash
were discarded. The montmorillonite treated in this manner
was retained as a slurry solution. The montmorillonite concen-
tration in this stock solution was determined by drying a
well-defined volume of the solution at 105°C until a constant
weight was obtained and by measuring the difference in
weight. The clay concentration of the stock solution was in the
range 20 ; 30g/liter.
Humic acid was prepared from sodium humate (Aldrich
Chemical Co.). The commercial sodium humate was first dis-
solved in deionized water and precipitated by adjusting the
solution pH to 1.5. The precipitate was redissolved in deion-
ized water. This solution was further purified by an ultrafiltra-
tion process. Ultrafree-15 filtration units, provided by the Mil-
lipore Company, were made of polysulfone membranes with
molecular weight cutoffs (MWCO) of 5,000 and 10,000. The
wall of the units was made of polycarbonate. They could fit
into 50-ml centrifuge tubes and achieve separation by centrif-
ugal force. The concentrate from the 10,000 MWCO mem-
brane filtration and the filtrate permeated through 5,000
MWCO membrane filtration was discarded. Following each
filtration, the concentrate was washed three times with deion-
ized water. The purified solution of humic acid was used as a
stock solution. The concentration in these solutions is ex-
pressed in terms of total carbon content as determined by
combustion analysis.
A 1000 ppm Cd(NO 3) 2, Cu(NO 3) 2, and Pb(NO 3) 2 standard
solution was purchased from Fisher Scientific. The concentra-
tion of this standard solution was guaranteed by the supplier
and was used both as a standard and as the metal solution for
the adsorption experiments. All other chemicals used were
reagent grade or better.
Adsorption Procedures
Batch adsorption was carried out by using 50-ml scaled
centrifuge tubes made out of polypropylene. As detailed in Fig.
1, the initial metal concentration was less than 5.0 3 10 25M.
Following mixing of the desired volume of stock solution, the
pH was adjusted by the addition of dilute HNO 3 or NaOH. The
final volume was adjusted using deionized water. The samples
were placed in an orbital shaker and shaken for 48 h at 25°C.
The samples were then centrifuged at 11,000 rpm for 20 min.
The supernatants were filtered using a 0.45-mm syringe filter.
Ten-milliliter aliquots of filtrate from each sample were acid-
ified using concentrated HNO 3 and stored in polypropylene
centrifuge tubes for analysis by atomic absorption. Additional
10-ml aliquots of filtrate were transferred into the ultrafiltration
unit equipped with a 5,000 MWCO polysulphone ultrafiltration
membrane to separate complexed metal ions from uncom-
plexed ions. The separation was carried out by centrifugation at
about 5,000 rpm (;2000 g). Humic acid concentrations were
determined following 0.45-mm syringe filter filtration.
To determine the reversibility of the adsorption of metal ions
on montmorillonite with or without the presence of humic acid,
the desorption properties were also tested. The montmorillonite
samples were taken from centrifuged samples containing the
adsorbed metals. The content of adsorbed metal was known
from analysis of the concentration of supernatant solution and
by calculations based on the mass balance. These solid samples
were redistributed in 0.1 M NaNO 3 solution. The pH was
adjusted to 4.0 through the addition of an NaAc–HAc buffer
solution. After being shaken for 5 h at room temperature, the
samples were centrifuged at 11,000 rpm for 15 min. The
supernatant was collected in a 50-ml volumetric flask. The
same procedure was repeated three times. Deionized water was
added to the flask which contained the collected supernatant
 ADSORPTION/DESORPTION ON CLAY MINERALS 227

FIG. 1. Schematic representation of experimental procedures.

until the 50-ml mark was reached. The supernatant solution
was analyzed using atomic adsorption to determine the metal
concentration. The desorption ratio was defined as the amount
of metal desorbed divided by amount of the metal originally
adsorbed.
Analyses
montmorillonite or humic acid was determined by mass bal-
ance.
RESULTS
The results of the adsorption of humic acid as a function of
solution pH and concentration are given in Tables 1 and 2. The

The concentration of metals in the aqueous phase was de-

termined by atomic absorption. A Perkin–Elmer model 500 TABLE 1
Atomic Absorption Spectrophotometer was used in these mea- The Adsorption of Humic Acid on Montmorillonite
surements by following the standard procedures and methods as a Function of pH a
established by the EPA. A calibration curve was determined
using standard samples prior to each measurement. Eq. conc. of HA Adsorbed c Percentage of adsorbed
b
Humic acid concentration was measured using a UV160 Eq. pH in solution c (mg/liter) (mg/g-mont) HA (%)
spectrophotometer at a wavelength of 400 nm. Pettersson et al. 2.37 9.42 26.19 93.29
(30) used the absorption at 250 nm to analyze the concentration 3.90 26.18 22.84 81.36
of humic acid. However, at this wavelength the absorption is 4.57 33.88 21.30 75.87
very sensitive to the NO 32 present in our samples. In order to 5.01 41.28 19.82 70.60
eliminate the effect of pH on the absorption, samples (usually 5.63 51.93 17.69 63.01
6.55 59.58 16.16 57.56
5 ml) for humic acid concentration analysis were mixed with a 6.82 63.28 15.42 54.93
2-ml NaAc–HAc buffer solution to stabilize the solution pH to 7.31 66.64 14.75 52.54
approximately 4.5. The concentration of humic acid was ex- 7.98 70.64 13.95 49.69
pressed as ppm carbon. The concentration in the stock solution a
of humic acid was determined by an EAGER 200 combustion Ionic strength was 0.1 M NaNO 3. Initial concentrations of HA and clay
were 140 mgC/liter and 5.0 g/liter, respectively.
elemental analyzer. The standard solution of humic acid was b
Equilibrium pH variation was 60.1.
obtained by diluting the stock solution of humic acid with a c
Average value of at least three measurements. The relative errors are less
known concentration. The amount of metal adsorbed on either than 8.0%.
228 LIU AND GONZALEZ

TABLE 2 The results of the isothermal adsorption of humic acid on

The Adsorption of Humic Acid on Montmorillonite as a montmorillonite at a constant pH of about 6.0 and ionic
Function of the Equilibrium Concentration of Humic Acid a strength of 0.1 M are given in Table 2. An increase in the
equilibrium concentration of humic acid results in an increase
Eq. conc. of HA in Adsorbed b Percentage of adsorbed
solution b (mg/liter) pH c
(mg/g-mont) HA (%) in the amount of adsorbed humic acid on montmorillonite.
Figure 2 shows the results of the adsorption of metals on
4.35 6.01 3.79 81.33 montmorillonite as a function of humic acid concentration in
8.67 5.84 7.62 81.48
the solid phase. This experiment was performed by first ad-
15.85 5.92 13.32 80.78
19.97 6.05 14.72 78.66 sorbing humic acid on the montmorillonite. The humic acid
31.08 5.88 16.94 73.16 adsorption was carried out by adding different amounts of
40.47 5.97 19.98 71.17 humic acid to the montmorillonite suspension. Initial concen-
69.09 6.02 23.62 63.09 trations of HA for a series of samples were in the range 10 to
99.13 5.93 26.97 57.64
300 mgC/liter. The pH and ionic strength were controlled at 3.0
a
Ionic strength was 0.1 M NaNO 3. Clay concentration was 5.0 g/liter. and 0.1 M, respectively. After separation by centrifugation, the
b
Average value of at least three measurements. The relative errors are less amount of humic acid adsorbed on montmorillonite was deter-
than 8.0%. mined and the precipitate was redistributed in the metal solu-
c
The pH variation was 60.1.
tion. The pH and the ionic strength in the process of metal
adsorption were controlled at 6.0 and 0.1 M, respectively. The
concentration of montmorillonite was 5.00 g/liter for all the desorption of humic acid under such conditions was not de-
data if not specified. The ionic strength was 0.1 M NaNO 3 for tectable by the UV-VIS method. Thus the amount of humic
all samples. The amount of adsorbed humic acid on the mont- acid desorption was neglected. A slight increase in the amount
morillonite decreased with increasing pH. The percentage of of adsorption was observed for Cd and Cu when the adsorbed
adsorbed HA was calculated by taking the adsorbed amount of humic acid was increased. But no measurable change in the
humic acid and dividing it by the total amount of humic acid amount of adsorbed Pb on montmorillonite was observed.
initially added. The percentage of adsorbed humic acid de- Two different adsorption sequences, preadsorption and co-
creased from about 93% at pH 2.37 to about 50% at a pH of adsorption, were examined. Preadsorption refers to the process
about 8.0. by which the montmorillonite used in the metal adsorption was

FIG. 2. Metal adsorption on montmorillonite in the presence of humic acid. The pH and ionic strength were controlled at 6.0 and 0.1 M, respectively.
 ADSORPTION/DESORPTION ON CLAY MINERALS
FIG. 3. Metal adsorption on montmorillonite as a function of adsorbed
humic acid. The pH and ionic strength were controlled at 6.0 and 0.1 M,
respectively. (top) Pb adsorption, (middle) Cd adsorption, (bottom) Cu adsorp-
tion. (F) preadsorption, (E) coadsorption.
FIG. 4. Adsorption of Pb and humic acid on montmorillonite as a function of ionic strength. Ionic strength was controlled with NaNO 3. Equilibrium pH was
6.5. Initial concentrations of HA and lead were 104 mgC/l and 5 3 10 25 M, respectively.
229
preequilibrated with the humic acid and the amount of humic
acid adsorbed was known. Coadsorption refers to the process
by which the metal, humic acid, and montmorillonite stock
solutions were mixed together simultaneously. The results of
the adsorption sequences on the metal adsorption are shown in
Fig. 3. No obvious difference between the two adsorption
processes is observed for Pb and Cd. For Cu, there is a slightly
higher amount of adsorption for the coadsorption process than
the preadsorption process.
The adsorption of humic acid and metals on montmorillonite
as a function of ionic strength is shown in Fig. 4. The set of
data were obtained by adding a different amount of 5 M
NaNO 3 solution to the samples containing the same initial
concentration of metals and humic acid. The equilibrium con-
centrations of metals and humic acid in the supernatant were
analyzed following centrifugation. An interesting observation
is that in the presence of humic acid, the amount of adsorbed
Pb on montmorillonite increases with increasing ionic strength.
Figure 5 shows the results of Pb adsorption as a function of
ionic strength at two different equilibrium pH values. It shows
that at a relatively high pH, e.g., when pH . 6.0, the amount
of adsorbed Pb increases with increasing ionic strength, which
is similar to the results shown in Fig. 4. But at a lower
equilibrium pH, an increase in the ionic strength results in a
decrease in the amount of adsorbed Pb on montmorillonite.
The effect of metals on the adsorption of humic acid on
montmorillonite is shown in Fig. 6. The adsorption of humic
230 LIU AND GONZALEZ

FIG. 5. Effect of ionic strength on Pb adsorption in the presence of humic acid.

acid on montmorillonite is compared for the three different DISCUSSION

metals studied. A slight increase in the amount of humic acid
adsorption on montmorillonite is observed when there are Humic Acid Adsorption on Montmorillonite
metals present in the system.
As shown in Table 1, an increase in pH from ;2.3 to ;8.0
Desorption of Cd, Pb, and Cu from montmorillonite as a
results in a 50% decrease in the amount of humic acid adsorbed
function of the adsorbed amount of humic acid are shown in
on montmorillonite. In this pH range, the surface of montmo-
Fig. 7. The original adsorption was carried out at pH 6.0 6 0.1
rillonite is negatively charged. The results of the zeta-potential
and an ionic strength I 5 0.1 M. The solid phase obtained
measurements show that the negative charge density on mont-
from centrifugation with a known amount of adsorbed metal
morillonite will increase with increasing pH. The same trend
and humic acid was used to carry out the desorption experi-
ment. The solid was redistributed in a solution of I 5 0.1 M
and buffered at pH 3.8. No obvious effect of adsorbed humic
acid on the desorption of the three metals tested was observed.

FIG. 7. Effect of humic acid on the desorption of metal ions from

FIG. 6. Effect of metal ions on humic acid adsorption on montmorillonite.
Initial metal concentrations were 5 3 10 25 M for all samples. Equilibrium pH
was controlled at 6.0 6 0.1.
montmorillonite. Adsorption was carried out at a pH 6.0 6 0.1 and ionic
strength I 5 0.1 M. The solid phase obtained from centrifugation with a
known amount of adsorbed metal was used to carry out the desorption
experiment. The solid was redistributed in a buffered solution at pH 3.8 and
I 5 0.1 M.
 ADSORPTION/DESORPTION ON CLAY MINERALS
occurs with the molecules of humic acid. The higher the pH,
the greater will be the dissociation of the functional groups
OCOOH and OCOH to OCOO 2 and OCO 2. The net effect
will result in an increase in negative charges on humic acid.
The electrostatic interaction between the charges will repel the
humic acid from the surface of montmorillonite.
There are three possible mechanisms governing the adsorp-
tion of humic acid on montmorillonite. They are cation bridg-
ing, water bridging, and H-bond complexation. At low pH,
H-bond complexation could be the dominant mechanism. At
higher pH, because of the dissociation of OCOOH and
OCOH, the molecules of humic acid become more hydro-
philic. At the same time, the adsorption of cations becomes
more significant at high pH, so that cation bridging becomes
the main mechanism. The mechanism of water bridging could
exist under conditions of both low and high pH.
Although the desorption of humic acid from montmorillonite
was not systematically investigated in this study, it has been
found that at a pH of ;4.0 and an ionic strength of 0.1 M, the
desorption of humic acid from montmorillonite is so small that
the UV-VIS method used to analyze the humic acid concen-
tration could not detect it. This observation illustrates either a
strong bond (e.g., H-bond) existing between the humic acid
and montmorillonite or that the humic acid molecules have
entered into the space between the layers of montmorillonite.
The Effect of Humic Acid on the Adsorption of Metals on
Montmorillonite
The effect of humic acid on metal adsorption was studied by
relating the amount of metal adsorbed on montmorillonite to
the amount of humic acid adsorbed. Only a slight increase in
the amount of metal adsorbed on montmorillonite was ob-
served for Cd and Cu when the amount of humic acid adsorbed
was increased (Fig. 2). Generally, this is contrary to the results
that minerals coated by humic acid have a higher capacity in
the adsorption of metal ions. Experimental results are available
for minerals such as kaolinite (11, 16, 31). However, no direct
data are available in the case of montmorillonite for compari-
son purposes. Using the results from the kaolinite studies as a
comparison with these from montmorillonite might be inap-
propriate due to differences in the structure of kaolinite and
montmorillonite.
As proposed by Leckie (32) and Stumm (2), there are two
possible structures for the adsorption of the metal and organic
complex compounds on mineral surfaces. One is the
S–Me–HA and the other is the S–HA–Me, where S represents
the adsorption site on the solid surface and Me is the metal ion.
From the adsorption data, HA has almost an order of magni-
tude higher adsorption capacity than montmorillonite. As
shown in Fig. 3, there is no significant difference in metal
adsorption between adsorption sequences, i.e., preadsorption
and coadsorption. The adsorption/desorption data in Fig. 6
prove that the existence of bivalent metal ions enhances the
231
adsorption of humic acid on montmorillonite. The desorption
rates of the three metals from montmorillonite have no signif-
icant change when the amount of humic acid adsorption is
increased (Fig. 7). Combining the overall data, the most pos-
sible surface structure should be S–Me–HA given sufficient
adsorption time and at a relatively high pH. Two possible
reasons might be proposed to explain the experimental results.
The first is that the metal ions are acting like a bridge (2)
between the humic acid and the montmorillonite. And the
second is that montmorillonite has a stronger affinity for the
bivalent metal ions than humic acid so that even the sites
pre-occupied by humic acid in montmorillonite could be finally
intercalated by metal ions.
The Effect of Ionic Strength on the Adsorption of Metal Ions
in the Presence of Humic Acid
Figure 4 demonstrates a simultaneous adsorption of Pb 21
and humic acid on montmorillonite as a function of ionic
strength at a pH of 6.5. It shows that increasing the ionic
strength results in an increase in the amount of lead ad-
sorbed, at the same time, resulting in a decrease in the
amount of humic acid adsorbed. This trend is the opposite of
results previously observed in this research. Other investi-
gators (6 –11) have observed that the amount of metal ad-
sorbed on montmorillonite decreased with increasing ionic
strength. The adsorption of humic acid decreased when
ionic strength was increased. At a lower pH, e.g., at a pH of
4.0 as shown in Fig. 5, the trend of lead adsorption is
reversed. The increase in ionic strength results in a decrease
in lead adsorption. At a higher pH, the humic acid tends to
be hydrophilic. An increase in the ionic strength results in
the reduction of the hydrodynamic thickness of adsorbed
humic acid (2) and compresses the thickness of the double
layer. The net effect would be beneficial for the penetration
of metal ions into the inner layer and adsorbtion directly on
the montmorillonite surface. On the other hand, there will be
more functional groups in humic acid protonated at lower
pH and the molecules of humic acid become more hydro-
phobic. In this situation, H-bonding might be the principle
mechanism for humic acid adsorption. Therefore, it would
be more difficult for the metal ions to intercalate. Increasing
the ionic strength will only cause more monovalent ions
(Na 1 in this study) to exist in the outer layer and cause a
decrease in the electrostatic potential to further decrease the
adsorption of the bivalent metal ions. More detailed exper-
iments are needed to fully recognize the environmental
significance of this result, which means that the presence of
natural organic materials might be environmentally benefi-
cial in keeping harmful metals adsorbed on the sediments
rather than remaining in solution. This might be an impor-
tant factor to be included in the investigation of water
pollution in estuaries.
232 LIU AND GONZALEZ

CONCLUSIONS 9. Millward, G. E., and Moore, R. M., Water Res. 16, 981 (1982).
10. Kooner, Z. S., Environ. Geology 21, 242 (1993).
Bivalent metal adsorption on montmorillonite remains un- 11. Fu, G., and Allen, H. E., Water Res. 26, 225 (1992).
changed in the presence of humic acid, except in the case of 12. Zhou, J. L., Rowland, S., Mantoura, R. F. C., and Braven J., Water Res. 28,
571 (1994).
adsorption as a function of ionic strength. An increase in lead
13. Davis, A. P., and Upadhyaya, M., Water Res. 30, 1894 (1996).
adsorption on montmorillonite was observed when the ionic 14. Greenland, D. J., Soil Sci. 111, 34 – 41 (1971).
strength was increased in the presence of humic acid. From the 15. Schnitzer, M., and Kodama, H., Science 153, 274 –277 (1966).
overall data, bivalent metal ions are most likely bridging be- 16. Nayak, D. C., Varadachari C., and Ghosh K., Soil Sci. 149, 268
tween the adsorption sites on montmorillonite and humic acid (1990).
molecules. Further studies on the system of metal ions, humic 17. Varadachari, C., Mondal, A. H., and Ghosh, K., Soil Sci. 151, 220 (1991);
Varadachari, C., Mondal, A. H., and Ghosh, K., Soil Biol. Biochem. 26,
acid, and clay minerals concerning the aggregation properties
1145 (1994); Varadachari, C., Mondal, A. H., and Ghosh, K., Soil Sci. 159,
as a function of pH and ionic strength are necessary to properly 185 (1995).
estimate the rate and distribution of heavy metal pollution in 18. Taylor, M. D., and Theng, B. K. G., Commun. Soil Sci. Plant Anal. 26, 765
the estuary regions. (1995).
19. Maguire, S., Pulford, I. D., Cook, G. T., and Mackenzie, A. B., J. Soil Sci.
ACKNOWLEDGMENTS 42, 599 (1992).
20. Lövgren, L., and Sjöberg, S., Water Res. 23, 327 (1989).
The authors acknowledge financial support from the U.S. Department of 21. Kerndorff, H., and Schnizer, M., Geochim. Cosmochim. Acta 44, 1701
Energy as a part of the Tulane/Xavier joint program on Hazardous Wastes in (1980).
the Aquatic Environment of the Mississippi River Basin. 22. O’Shea, T. A., and Mancy, K. H., Water Res. 12, 703 (1978).
23. Saar, R. A., and Weber, J. H., Can. J. Chem. 57, 1263 (1979); Saar, R. A.,
and Weber, J. H., Environ. Sci. Technol. 14, 877 (1980).
REFERENCES
24. Buffle, J., Greter, F., and Haerdi, W., Anal. Chem. 49, 216 (1977).
1. Grim, R. E., “Clay Mineralogy.” New York, McGraw–Hill, 1968. 25. Aualiitia, T. U., and Pickbering, W. F., Water Res. 20, 1397 (1986).
2. Stumm, W., “Chemistry of the Solid–Water Interface.” Wiley, New York, 26. Mota, A. M., Rato A., Brazia, C., and Goncalves, M. L. S., Environ. Sci.
1992. Technol. 30, 1970 (1996).
3. Suffet, I. H., and MacCarthy, P., “Aquatic Humic Substances.” Am. 27. Malcolm, R. L., and MacCarthy, P., Environ. Sci. Technol. 20, 904
Chem. Soc. Washington, DC, 1989. (1986).
4. Sposito, G., Critical Rev. Environ. Control 16, 193 (1986). 28. Hering, J. G., and Morel, F. M. M., Environ. Sci. Technol. 22, 1234
5. Thurman, E. M., and Malcolm, R. L., Environ. Sci. Technol. 15, 463 (1988).
(1981). 29. Miller, S. E., Heath, G. R., and Gonzalez, R. D., Clays Clay Miner. 30, 111
6. Hohl, H., and Stumm, W., J. Colloid Interface Sci. 55, 281 (1976). (1982).
7. Davis, J. A., and. Leckie, J. O., J. Colloid interface Sci. 63, 480 (1978). 30. Pettersson, S., Häkansson, K., and Allard, B., Water Res. 27, 863 (1993).
8. Benjamin, M. M., and Leckie, J. O., J. Colloid Interface Sci. 83, 410 31. Schulthess, C. P., and Huang, C. P., Soil Sci. Soc. Am. J. 55, 34 (1991).
(1981). 32. Leckie, J. O., OECD, 183 (1995).