Aust. J. Chem.

, 1977, 30, 1417-22

The Sorption of Lead and Cadmium

Species by Clay Minerals

Helen Farrah and William 10. Pickering

Chemistry Department, University of Newcastle, N.S.W. 2308.

Abstract
The effect of pH changes and the presence of ligands on the uptake of lead and cadmium ions by
three types of clay mineral (kaolinite, illite and montmorillonite) has been investigated,
In the absence of ligands, metal ion adsorption increases gradually with increasing pH until a
threshold pH value is exceeded, whereupon total precipitation/sorption (attributed to formation of
hydroxy species) occurs. With ligands present, the threshold point tends to shift to higher pH values,
the magnitude of the effect depending on the stability of the metal complex formed. Adsorption
of cationic metal complexes is subject to competition from charged protonated ligand species;
anionic complexes are not sorbed.

Introduction
It has been shown112that the amount of copper or zinc ion sorbed by a clay is
determined by several factors, including solution pH and the concentration and
nature of any ligands present. Minimal uptake of these metal ions occurs when they
are present as anionic complexes, or when significant amounts of competing cationic
species (e.g. protonated solvent or ligand; other divalent ions3) are present.
In the absence of ligands, sparingly soluble hydroxy species are formed when the
solution pH exceeds a threshold value (c. 6); the magnitude of this value is lowered
slightly in the presence of clay.
Analogy (based on solution chemistry) suggests that lead and cadmium ions
should exhibit behaviour similar to that observed with copper and zinc but published
data create doubts. For example, lead should be totally precipitated at pH 8, yet
it has been reported4 that in the presence of illite and montmorillonite less lead is
lost from solution at this pH than at pH 6 or 7. By contrast, in the presence of oxide
surfaces such as TiO, or cc-FeOOH complete removal of cadmium from solution
(due to combination of precipitation and sorption) has been observed5 at pH values
two or three units less than predicted from solubility product calculations.
The fixation of lead and cadmium species to the clay components of soils and
stream sediments is a process of some significance, since it can influence the amount
of toxic metal ion available to living matter. Accordingly, it seemed appropriate
Farrah, H., and Pickering, W. F., Aust. J. Chem., 1976, 29, 1167.
Farrah, H., and Pickering, W. F., Aust. J. Chem., 1976, 29, 1649.
Farrah, H., and Pickering, W. F., Water, Air, Soil Pollut., in press.
Hildebrand, E. E., and Blurn, W. E., Natuvwissenschaften, 1974, 61, 169.
James, R. O., Stiglich, P. J., and Healy, T. W., Discuss. Faraday Soc., 1975, 59, 142.
 H. Farrah and W. F.Pickering

to examine the effect of pH and selected ligands on the loss of lead or cadmium ions
from solution, in the presence of three different types of clay.

Experimental
Kaolinite from Home Rule, N.S.W., was kindly supplied by Dr Hunter. Illite (from Morris,
Illinois) and montmorillonite (from Polkville, Mississippi) were purchased from Wards Natural
Science Establishment.
Finely ground samples of clay were purified and converted into the sodium form by a method
similar to that reported by Posner and Q ~ i r k . The ~ < 2 pm fractions were dialysed to remove
excess electrolyte and diluted to about 0.15 % (w/v) with deionized water.
In the adsorption studies 5-ml aliquots of the suspension (10-ml aliquots for kaolinite) were
adjusted to various pH values by the addition of nitric acid or sodium hydroxide. Appropriate
volumes of water, ligand and metal nitrate solution were then added to give a final volume of 30 ml.
The solutions, contained in sealed glass containers, were mixed for over 24 h in a stirrer device
while immersed in a water bath held at 25.0+0.1°C.
After mixing, the sample tubes were centrifuged, and if some cloudiness persisted (suspended
matter leads to erroneous atomic absorption readings) the solutions were filtered through a 0.45-pm
membrane filter. The pH of the clear solutions was measured and the total metal concentration
subsequently determined by atomic absorption spectrophotometry. The instrument used was a
Varian-Techtron AA5 atomic absorption unit. Measurements were made using an air-acetylene
flame and appropriate resonance lines (217.0 nm for lead, 228.8 nm for cadmium). The amount
of metal species adsorbed by the clay was calculated from the change in solution concentration.
In the ligand effect studies, the initial metal ion concentration* was held at around 1.7 x M
and the pH was varied between 3 and 11 (at least 10 different values). The ligands used were selected
because of their ability to convert the ions into complex species of varying size, charge and stability.
In each test, the loss of metal ion from solution was reported as mmol sorbed per kg clay,
irrespective of the process involved. The values reported for alkaline test solutions thus represent
the sum of the amount adsorbed and the amount precipitated.

Results
The effect of pH on the amount of lead or cadmium removed from solution in
the presence of dilute clay suspensions (c. 250 mg/l) and a range of ligands is shown in
Figs 1 and 2. Since loss of these ions can be attributed to adsorption and/or precipita-
tion, it is necessary to consider the effect of solution variables on both these processes.
Several different situations can be identified.
Curves A (Fig. 1) and B (Fig. 2) represent systems in which the presence of the
ligand has little significant effect on the behaviour of the clay-solute system, i.e.
the amount of metal ion adsorbed by the clay increases gradually as the pH is increased
from 3 to 6; at higher pH values the residual metal ion is precipitated as sparingly
soluble hydroxy species.
Calculations based on published data7 clearly demonstrate that the ability of a
ligand to prevent (i.e. 'mask') this precipitation reaction depends on the stability
of the metal-ligand complex, the relative concentrations and solution pH.
The interplay of the various contributing factors is quite apparent in some of the
systems examined in this study. For example, a glycine : lead ratio of 6 : 1 was
insufficient for effective masking, and the metal hydroxy species precipitated at a
* Adsorption isotherm studies showed that, at a given pH (e.g. c. 5), the amount adsorbed became
constant when the initial solution concentration was > lo-" M.
Posner, A. M., and Quirk, J. P., Puoc. R. Soc. London, Ser. A, 1964, 278, 35.
Sillen, L. G., and Martell, A. E., 'Stability Constants of Metal-Ion Complexes' Spec. Publs Nos
17 and 25 (The Chemical Society: London 1964).
 Sorption of Lead and Cadmium by Clay Minerals 1419

100 , montmorillonite

pH of solution

Fig. 1. The effect of pH and chemical form on the uptake of lead species by clay minerals. Initial
lead concentrations, 1 . 7 x M. Clay suspension concentrations (w/v): kaolinite, 0.05 %;
illite and montmorillonite, 0.025%. Sorption observed in presence of: A, glycine (ratio
Pb : Gly = 1 : 6); B, tartrate (ratio Pb : tart = 1 : 5); E, nitrilotriacetic acid (ratio Pb : nta = 5 : 6).
Circles indicate the position of the lead precipitation region in the absence of ligands. s, precipitation
region for hydroxy species, clay absent.

kaolin montmorillonite

600 - /'--"-

400 -

300 -
/
d'" L
/f
200 -
Ic

pH of solution

Fig. 2. The effect of pH and chemical form on the uptake of cadmium species by clay minerals.
Initial cadmium concentrations, 1 . 7 x M. Clay suspension concentrations (w/v): kaolinite,
0.05 %; illite and montmorillonite, 0.025 %. Sorption in presence of: A, glycine (Cd : Gly = 1 : 6);
B, tartrate (Cd : tart = 1 : 5); c, ethylenediamine (Cd : en = 1 : 6); D, cc,af-bipyridyl(Cd : bpy =
1 : 6); E, nitrilotriacetic acid (Cd : nta = 5 : 6); F, cyanide (Cd : CN- = 1 : 6). Circles
indicate the position of the cadmium precipitation region in the absence of ligands. S, precipitation
region for hydroxy species, clay absent.
 H. Farrah and W. F. Pickering

pH similar to that observed in the absence of ligands (Fig. 1, curve A). A similar
excess of glycine in cadmium solutions resulted in precipitation of the metal ion
being deferred until the pH was approximately two units higher than that observed
in the ligand-free system (cf. curves A and B, Fig. 2); in other words, formation of
the cadmium glycinate species resulted in extension of cationic adsorption into the
alkaline region. The stability constants of cadmium and lead glycinate complexes
are similar in magnitude, hence the different behaviour has to be attributed to
differences in solubility product values.
With tartrate as the ligand species, there are differences in the stability of the two
metal complexes. A 5 : 1 addition of tartrate ion to cadmium solutions had minimal
masking effect (Fig. 2, B); in the case of lead (Fig. 1, B) precipitation of the hydroxy
species was inhibited. At the same time, large losses of lead from solution were
observed at pH >7, a loss attributable to the limited solubility of lead tartrate
(7 x mol/l. at 25"). This species is soluble in alkali and this is reflected in a
decrease in the amount lost at higher pH values.
Ethylenediamine and cr,al-bipyridyl both form stable cationic complexes with
cadmium (p, c. 12.5 and 10.5 respectively; values vary with experimental parameters
including ionic strength and temperature) and as shown in Fig. 2 (curves' c and D)
the presence of an excess of these ligands (ratio 6 : 1) shifts the precipitation zone to
higher pH values. At the same time, differences in ligand basicity have a profound
effect on the 'adsorption' component of the total metal loss from solution.
With bipyridyl (log K, c. 4.5) competition for adsorption sites attributable to
the presence of protonated ligand should become minimal at pH >5. As shown by
curve D, masking is effective up to pH 10 and adsorption of the cationic complex
occurs in increasing amounts up to the precipitation zone.
The situation with ethylenediamine is somewhat different, due mainly to the high
degree of protonation that persists into the alkaline range (e.g. at pH 8, approximately
30% e i ~ H , ~and
+ 70% enH'). Not only is the effectiveness of 'masking' reduced,
but the apparent affinity of clays for these species results in little metal ion being
adsorbed from solutions having a pH < 6 (cf. Fig. 2, c).
Clays appear to have little affinity for stable anionic metal complexes, since the
presence of a ligand capable of forming such complexes can result in minimal sorption
and precipitation of metal ion.
As shown by the results obtained with nitrilotriacetate (nta) as the model ligand
(cf. Figs 1 and 2, curves E) pH can be a significant variable. The stability of the heavy
metal ion-nta complexes (log K, c. 10 for cadmium; c. 11.5 for lead) is such that a
slight excess of ligand (e.g. 6 : 5) reduced the metal ion loss to near zero over a
limited pH range only. At pH < 7, the clays successfully competed against the ligand
for metal ions (the effective complexing power of the ligand being reduced by
protonation as the pH is decreased). At high pH, the stability of the complex was not
sufficient to prevent some precipitate formation. The pH region in which minimal
loss of metal ion from solution occurred could be broadened by using a larger excess
of nta or a more reactive ligand (e.g. edta).
The effect of cyanide ion additions on cadmium behaviour (Fig. 2, F) highlights
the fact that one must consider the stability of the species formed by the ligand with
both metal ion and hydrogen ions. In this example, the magnitude of the cumulative
constant (P,) for the tetracyanocadmium(r~)ion is such that an excess of ligand
Sorption of Lead and Cadmium by Clay Minerals

(e.g. L : M = 6 : 1) should ensure effective masking of the cadmium hydroxide

precipitation reaction up to high pH values. However, due to the affinity of the clays
for the cadmium ion, the weak acid nature of HCN, and the stepwise addition of
ligand to metal ion, zero loss of cadmium ion from solution occurred only at pH < 9.
With all clays, the presence of cyanide appeared to have little effect on adsorption
up to pH 7; beyond this point uptake fell to zero.

Discussion
In general, the results obtained were of the type expected on the basis of previous
studies with copper and zinc salts.
In all these systems, it proved extremely difficult to rigorously separate adsorption
effects from solution reactions such as precipitate formation. Loss of metal ions by
precipitation is not restricted to hydroxy compounds. The formation of lead tartrate
has been mentioned above, and it has been noted3 previously that, at pH 4, the
presence of excess sulphate or phosphate ion can cause precipitation of most of the
lead ion present in a clay-solute system.
The role of hydroxyl ions appears to be multiple. In the absence of ligands having
a strong affinity for the metal ions, adding a base leads to the formation of sparingly
soluble hydroxy metal complexes. In the presence of clay, total precipitation occurs
at a slightly lower pH (circles on Figs 1 and 2) than in blank solution tests (curves s).
In the region of partial precipitation the term pM +pOH is c o n ~ t a n t . This
~ type of
relationship is consistent with the formula of the sparingly soluble species being
M,(OH),x'. At least seven different lead species are considereds to be formed in
alkaline media including PbOH' and P ~ , ( O H ) , ~+.
The lower solution pH associated with formation of hydroxy species in the presence
of clay has been attributed to adsorption of hydroxyl ions by the suspended material,
thus yielding a higher surface pH value. Adsorption of hydroxyl ions is also con-
sidered3 to be responsible for the increase in total amount adsorbed as the pH is
increased from 3 to 6, either through acting as bridges to metal ions or through
proton abstraction from functional groups. Logarithmic plots of amount of metal
ion adsorbed against hydroxyl ion concentration yield lines of slope c. 0.07 (for
montmorillonite) or c. 0.25 (for kaolinite and illite) (for all four metal ions, lead,
cadmium, copper and zinc). These results imply that the amount sorbed varies
with OH]^"^ (or, on montmorillonite, [OH]' 07). In those cases where precipitation
of metal ion is prevented through formation of cationic complexes (e.g. curves A
and D, Fig. 2), this power relationship with respect to hydroxyl ion concentration
continues into alkaline media. Several different mechanisms have been proposed5
for the adsorption of hydroxy species at metal oxidelwater surfaces, but to date it
has not proved possible to formally resolve the nature of the processes associated
with sorption of heavy metal ions on the various clays. As discussed in previous
much of the behaviour on montmorillonite can be interpreted in
terms of a simple cation exchange process, but even this generalization has to be
modified to account for the apparent high affinity to nitrogen-containing ligands
by this clay. Kaolin and illite behave in a manner which suggests that competitive
adsorption (rather than stoichiometric ion exchange) is the predominant process.
Olin, A., Acta Chem. Stand., 1960, 14, 126, 814 and 1999.
 H. Farrah and W. F. Pickering

Environmental Aspects
Because of the environmental significance of lead and cadmium distributions,
it may be appropriate to attempt some extrapolation into the realm of natural systems.
The concentrations of lead and cadmium ions found in natural waters are usually
several orders of magnitude less than the initial concentrations used in this study.
This may indicate that the input is very small or that the bulk has been precipitated.
The fraction of initial input held by simple adsorption by pure clay minerals is pre-
dicted to be very small, due to factors such as low initial concentration (adsorption
isotherm effect), competition from other cations (e.g. calcium, magnesium, iron,
aluminium), and the possibility of stable anionic complex formation.
On the other hand, clay components of soils and sediments may contribute to
'reservoir' effects through acting as a support for hydroxide precipitation or as an
adsorbent for humic acids.
Humate sorption can be describedg by an equation of the form y = axb where y
is the amount of humic acid sorbed, x is the equilibrium concentration in solution,
and a and b are coefficients. Lead and cadmium fixation by humic acids has been
observed to decrease with decreasing and desorption experiments indicate
that about half of the adsorbed cadmium is present in an exchangeable form; the
other half is held as a coordination complex.
In a natural system many types of substrate (e.g. silica, clays, hydrated metal
oxides, organic matter) can be present in widely varying proportions, and it would
appear that accurate prediction of pH or ligand effects will prove feasible only when
more is known about all the various component systems.

Acknowledgment
We gratefully acknowledge the support provided for this project by the Australian
Research Grants Committee.

Manuscript received 1 November 1976

Orlov, D. S., and Pivovarova, I. A., Pochvooedenie, 1974,29, 59.

'O Hildebrand, E. E., and Blum, W. E., Naturwissenschafien, 1974, 61, 128.
Riffaldi, R., and Levi-Minzi, R., Water, Air, Soil Pollut., 1975, 5, 179.