Chapter 10

Influence of pH, Metal

Concentration, and Soil
Component Removal on
Retention of Pb and Cu by
an lUitic Soil

R a y m o n d N . Yong^ and Elaine M. MacDonald^

^Geoenvironmental Engineering Research Centre, Cardiff School of Engineering,
University of Wales, Cardiff, United Kingdom; ^Department of Civil Engineering, McGill
University, Montreal, Quebec, Canada

This study presents results and analyses on the effect of p H and initial
metal (Pb and Cu) concentration on retention of metals by an illitic clay
soil containing some natural organic material, carbonates, and oxides.
Soil suspension experiments w^ere conducted over a wide range of met-
al concentrations (0.25 to 50 mmol-L~^) at the natural soil p H values
and at p H values belowr the precipitation p H of the metals. At the natu-
ral soil p H values, sorption experiments demonstrated the expected ef-
fect of the high retention capacity of the soil. At lower p H values the
results obtained showed reductions in retention as high as 90% be-
cause of diminishing metal precipitation. While removal of the car-
bonates from the soil did not significantly change heavy metal reten-
tion, the removal of amorphous oxides from the soil resulted in
increased retention capacities which were at least two to three times
greater than those of the original soil. This is a result of the removal of
amorphous coatings of the minerals, thus permitting adsorption on the
previously masked negatively charged surfaces. In addition, the posi-
tively charged surfaces of the amorphous oxides (at p H levels below
Adsorption of Metals by Geomedia
Copyright © 1998 by Academic Press. All rights of reproduction in any form reserved. 229
230 Yong and MacDonald

their zero point of charge) complete with the metals ions for the nega-
tively charged sites, and have apparently severely reduced the metal
retention capacity of the soil. Pb distribution among the soil compo-
nents was analyzed using sequential extraction, and the carbonate
component was found to contain most of the retained Pb.

I. INTRODUCTION
The presence of heavy-metal-contaminated soils and sediments has been re-
ported in many studies (Yong et al.y 1992b; Allen et al, 1995). Sources of such
contaminants are generally anthropogenically derived. The following is a set of
examples which record the many instances and sources of contamination. Ravi-
shankar et al. (1994) reported Cu concentrations in Quebec sewage sludges rang-
ing from 139 to 7510 mg-kg~\ and studies reported by Salomons and Forstner
(1984) on the Ruhr river which flows through a heavily populated and industrial
region in which approximately 300 metal plating plants are situated among other
industries found that 55% of the heavy metals in the river came from industrial
and municipal sources. MuUer et al. (1994) reported concentrations of Pb above
10,000 mg-kg~^ in Austrian river sediments due to mining and ore smelting ac-
tivities upstream. Gobiel etal. (1994) traced anthropogenic Pb in the St. Lawrence
Estuary sediments to industrial Pb used as an additive in gasoline. Research by Shu
and Liu (1994) linked Pb contamination in Taiwanese rice paddies to two plasti-
cizer plants in the vicinity. Analyses of the Superfund Sites, where Pb and Cu have
been found to be common pollutants, showed the following list of sources: land-
fill/chemical waste dumps, metal finishing/plating and electronics, chemical phar-
maceuticals, mining/ore processing/smelting, battery recycling, oil and solvent re-
cycling, and paint (Allen et al, 1995).
Removal of heavy metals from soil porewater occurs by mechanisms such as
adsorption, complexation, precipitation, and filtration. However, sediments and
soils are neither permanent nor irreversible sinks for contaminants and may be-
come sources of contamination to surface water and groundwater when changes
in the local environment occur (Farrah and Pickering, 1978; Grambell et al, 1991;
Saeki, 1993).
The availability and mobility of heavy metals depend on their association with
soil components. Some retained contaminants may still be bioavailable (Luoma,
1989; Calmano et al, 1992). The two major sets of concerns in respect to assess-
ment of soil or sediment contamination include: (1) evaluation of the "storage" ca-
pacity (for contaminants) of the soils or sediments, and the potential for "mobi-
lization" or release of contaminants into the immediate environment, and (2)
Pb and Cu Retention 231

development of an efficient strategy for removal of the contaminants that would

be compatible with the manner in which the contaminants are retained in soils or
sediments. In both sets of interests, evaluation of the fate of the pollutants involves
determination or assessment of the distribution of the contaminants, i.e., charac-
terization of the contaminants contained in soils, and the manner in which these
are "held" or distributed in the soils, i.e., "bonded" to the various soil fractions
(soil minerals, amorphous materials, and soil organic matter). One recognizes that
the presence of inorganic and aqueous organic ligands in the soil system will com-
pete with the adsorption sites from the soil fractions for contaminants. In addition,
changes in the soil environment can alter the fate of the contaminants in the soil,
and in the case of heavy metal pollutants, it is understood that redox and pH con-
ditions will control and affect the chemical forms and mobility of the heavy met-
als (Grambell et al, 1991; Saeki et aL, 1993).
A large body of research is available on heavy metal retention mechanisms of
individual soil components. However, it is not possible at present to predict ad-
sorption in a multicomponent system (Bassett and Melchior, 1990). Honeyman
and Santschi (1988) explain that retention is only predictable in simple systems
such as a single oxide. Further, it is difficult to decipher between retention by pre-
cipitation and retention by adsorption (Sposito, 1989). Much effort to model the
behavior of contaminants in sediments and soils has represented the multicompo-
nent system either by some average collective property or as a collection of dis-
crete pure solid phases, a concept referred to as adsorptive additivity (Anderson
and Benjamin, 1990; Bassett and Melchior, 1990). However, many researchers
have reported nonadditive results from soil adsorption studies. Honeyman found
that particle interaction in binary suspensions of oxides can lead to significant de-
viations from the adsorptive additivity concept (Anderson and Benjamin, 1990).
Anderson and Benjamin (1990) reported that in some cases the addition of a sec-
ond adsorbent decreased the overall adsorption and explain that a unified model
must describe both the adsorption results and the changes in the physical charac-
teristics of the soil. They then went on to successfully model a mixed oxide sys-
tem by describing particle interactions and how those interactions influence the
surface chemistry of the system—an approach which has been identified as modi-
fied adsorption additivity.
Farrah and Pickering (1978) identified four possible mechanisms that may mo-
bilize heavy metals in soils: (1) changing acidity, (2) changing the system ionic
strength, (3) changing the oxidation reduction potential, and (4) the formation of
complexes. These findings stress the importance of identifying and understanding
the mechanism of retention in an aqueous soil environment, be it surface water
sediments, soil-groundwater systems, or landfill clay liners. The mechanisms and
processes involved in heavy metal retention include precipitation as a solid phase
(oxide, hydroxides, carbonates), ion exchange adsorption, and complexation re-
actions (Harter, 1979; Yanful et a/., 1988; Farrah and Pickering, 1977, 1979;
232 Yong and MacDonald

Maguire et ah, 1981; Yong et ai, 1990). The research linking pH and heavy met-
al retention in soils is well documented and consistently shows increased retention
with increased pH (Allard et al, 1991; Farrah and Pickering, 1977, 1979; Frost
and Griffin, 1977; Harter, 1983; Maguire et ai, 1981; Phadungchewit, 1990).
Whereas the mechanisms of retention may not always be defined by the re-
searchers, most recognize the importance of precipitation, showing that as pH in-
creases heavy metal solubility decreases (Allard et al, 1991; Jeffery and Uren,
1983; Harter, 1983).
The previous studies reported by Yong and Phadungchewit (1993) and Yong et
al. (1992b) examined the distribution of heavy metal contaminants among the soil
constituents using selective sequential extraction techniques. Because the associ-
ation of contaminants with each soil fraction—as determined by the selective se-
quential extraction technique—is in essence operationally defined, the previous
studies are somewhat constrained because of the extraction techniques used. In this
present experimental study, heavy metal (Pb and Cu) "contamination" of an illitic
silty clay soil is examined in its natural state, and also under conditions where the
carbonates and oxides have been removed from the soil before "contamination."
With this selective contamination technique, the contribution of soil components
such as carbonates and amorphous oxides to heavy metal retention and soil prop-
erties under various initial pH conditions and metal concentrations can be exam-
ined without the constraints associated with the previous studies. Retention of the
Pb and Cu by the untreated silty clay soil (no extraction of carbonates and oxides)
is examined in relation to comparable retention by the soil with carbonates and ox-
ides removed. The experiments are conducted using soil suspensions with varying
initial pH conditions and initial metal concentrations. A sequential extraction pro-
cedure was used to determine the distribution of Pb among the operationally de-
fined soil components in the untreated soil and compared to the retention obtained
when soil components are extracted prior to Pb contamination.

11. MATERIALS AND METHODS

A. SOIL COMPONENTS AND PROPERTIES

The soil used in the study was a silty clay surrogate soil obtained from a pul-
verized shale and marketed commercially under the trade name of Domtar Seal-
bond. The choice of the pulverized shale soil was predicated on the fact that it con-
tained most of the soil fractions found in the clay soils common in Eastern Canada.
Because of the need to obtain replicate samples, the pulverized shale soil also
served as a very useful source that was consistent in its composition as shown by
many studies which have benefited from its use (Yong et al., 1990, 1992a, 1993;
Yong and Phadungchewit, 1993).
Pb and Cu Retention 233

Table I
Untreated Soil (Sealbond) Composition
Mineral composition (in order of decreasing abundance) lUite, chlorite, quartz,
feldspar, and calcite
Carbonates (mean % by weight with standard deviation) 5.7 ± 0.3
Fe, Al, Si, and Mn amorphous oxides, hydroxides, and oxyhydroxides 1.2 ± 0.03
(mean % by weight of oxide with standard deviation)
Natural organic material (mean % by weight with standard deviation) 0.7 ± 0.09

Characterization of the surrogate soil included tests for determination of min-

eral composition, amorphous materials, carbonates, organic matter, pH, specific
surface area (S^), and cation exchange capacity (CEC). The X-ray diffraction stud-
ies were conducted using the techniques described by Starkley et al. (1984), and
amorphous materials determination was implemented using oxalic acid extraction
according to the method described by Kersten and Forstner, (1989). Carbonate
content was determined using 1N HCl to dissolve the carbonates, which were then
titrated with NaOH (Hesse, 1971); pH was measured in a 1:10 mass ratio of soil
to distilled water. The S^ was determined using ethylene glycol monoethyl ether
(EGME) saturation according to the procedure described by Eltantaway and
Arnold (1973), and CEC was measured using the BaCl^ method described by Hen-
dershot et al. (1993). The results of these characterization procedures are shown
in Tables I and II.
Soil carbonates were extracted from the soil using 1 M NaOAc adjusted to pH
5 with HO Ac at a 1 to 40 soil to solution ratio for a contact period of 5 hr, similar
to the procedure reported by Tessier et al. (1979) and Kertsen and Forstner (1989).
Previous studies indicate that the buffering capacity of the NaOAc-HOAc ex-
tracting solution was sufficient to dissolve all the CaC03 in carbonate-rich sedi-
ment samples. To ensure that all the carbonates had been extracted, the soils were
tested for presence of carbonates after completion of the extraction procedure us-

Table II
Properties of Untreated and Treated Soils
CEC SA pH
(M0-2meq-g-i) (m^-g-i) (1:10 soiliwater)

Untreated soil 23 ± 1.3 131 8.2

Soil treated for carbonate extraction 8 ±0.6 150 7.6
Soil treated for carbonate and oxide extractions 10 ± 0.3 116 ± 7.4 7.2

Note. Values are means with standard deviations.

234 Yong and MacDonald

ing the titration method described by Hesse (1971). The effect of extraction of car-
bonates on measured soil properties is shown in Table 11. Changes in the soil re-
dox conditions during extraction procedures may result in the release of compo-
nents that are not targeted, such as iron and manganese oxides (Rapin et al, 1986).
Typically this occurs when anoxic soils are exposed to atmospheric oxygen dur-
ing extraction procedures. Given the oxic conditions under which the soil used in
this study has been obtained, stored, and treated, this was not foreseen as a possi-
ble source of error.
In the case of the amorphous oxides, extraction was performed by the use of 0.1
mol*L~ ^ oxalic acid, buffered to pH 3 by ammonium oxalate, and mixed in the dark
at a 1 to 40 soil to solution mass ratio for 5 hr. Kersten and Forstner (1989) described
the acidified ammonium oxalate buffer solution as particularly selective toward iron
oxides with an ability to attack amorphous Al compounds. To remove the extract-
ed soil components and the extractants, the soil was washed three times with dis-
tilled water after each extraction. Liquid-solid separation was effected through cen-
trifugation for 10 min at 10,000 rpm where the radial distance from the center of
the rotor to the top of centrifuge tube was 4.5 cm and the radial distance from the
center of the rotor to the bottom of centrifuge tube was 5.5 cm. The effect of ex-
traction of carbonates and oxides on measured soil properties is shown in Table II.

B. SOIL SUSPENSION TESTS

Two general types of soil suspension tests were performed as part of this study.
The first involved an initial adjustment of all soil suspensions to a constant pH pri-
or to the addition of heavy metal solutions. These tests were conducted in two steps
over a 48-hr period in which the first 24 hr was designated as a pH adjustment pe-
riod. During this period, the soil was mixed with distilled water and the appropri-
ate amount of HNO3 at a soil to solution mass ratio of 1 to 6.67 and allowed to equi-
librate. The second 24-hr period was used to establish heavy metal contact, at which
point the appropriate amounts of Pb or Cu nitrate solution and distilled water were
added to the soil solution to bring the final soil to solution mass ratio up to 1 to 10.
The second type of soil suspension test was performed to examine the effect of
final pH at a constant initial concentration of Pb. The first 24 hr was designated as
a pH adjustment period; however, rather than adding the appropriate amount of
acid to reach a single desired initial pH, solutions of varying HNO3 or NaOH con-
centration were added to the soil to obtain final pH values ranging between 3 and
8. After completion of the 24-hr pH adjustment, an appropriate amount of Pb ni-
trate solution, adjusted to pH 4 with HNO3, was added to the soil suspension to
raise the final soil to solution mass ratio to 1 to 10 and the total concentration of
Pb to 5 mmol*L~^
Stock heavy metal solutions were prepared from the following nitrate forms of
Pb and Cu Retention 235

each metal: Pb(N03)2 and Cu(N03)2-2.5H20. All heavy metal solutions were ad-
justed to pH 4 using HNO3. To allow for escape of gases produced by carbonate
dissolution in the pH-adjusted soil suspension tests on the untreated soil, jar tests
were conducted using a high-speed bench stirrer set at 250 rpm to mix the soil sus-
pensions. Soil suspension tests performed with soil treated for carbonate extraction
were conducted in closed vessels mixed on a horizontal shaker. At the end of the
total 48-hr period, the solution was separated through centrifugation as described
in Section II.A, and the metal concentration in the supematants was measured by
atomic adsorption spectroscopy (AAS). For both types of soil suspension tests, ran-
dom duplicates were conducted as indicated on the figures presenting the results.

C. SEQUENTIAL EXTRACTION TESTS

The soil residue from the suspension tests performed at variable pH values but
at a constant initial Pb concentration (the second type from Section II.B) was used
as the material in the sequential extraction analyses. In this experiment, a sequen-
tial extraction method was used to obtain information on the distribution of Pb
among the operationally defined soil components. Where possible the same ex-
traction technique was used as that for soil components studied by extraction pri-
or to contamination (Section II.A). Efforts were made to select extraction proce-
dures least likely to affect the other soil components.
The soil residues were dried, and samples of approximately 0.75 g were re-
tained for sequential extraction analysis. The samples were first washed with dis-
tilled water and centrifuged, and the wash water was discarded. The soil was then
subjected to the following sequential extraction procedures:
1. Exchangeable. The soil was extracted for 1 hr at room temperature with 8
ml of magnesium chloride solution (1 mol-L~^ MgCl^, pH 7) with continuous ag-
itation (Tessier et al, 1979).
2. Carbonate Bound. The residue from step 1 was leached at room temperature
for a contact period of 5 hr with 30 ml of 1 mol*L~^ sodium acetate (NaOAc) ad-
justed to pH 5 with acetic acid (HOAc) under continuous agitation, similar to the
procedure reported by Tessier et al. (1979).
3. Oxide Bound. The residue from step 2 was leached at room temperature us-
ing 30 ml of 0.1 mol-L"^ oxalic acid (H^C^O^), buffered to pH 3 by ammonium
oxalate ((NH4)2C204), and continuously agitated in the dark for 5 hr (Kersten and
Forstner, 1989).
4. Bound by Natural Organic Matter. The residue from step 3 was leached in a
boiling water bath for 30 min with 8 ml of 5% sodium hypochlorite (NaOCl) ad-
justed to pH 9 with hydrochloric acid (HCl) (Shuman, 1983; Kersten and Forst-
ner, 1989).
236 Yong and MacDonald

5. Residual. The residue from step 4 was subjected to an acid digestion proce-
dure referred to as Method 3050 by the USEPA (1986). The soil is subjected to ni-
tric acid (HNO3) addition and heated to 95°C, followed by the addition of hydro-
gen peroxide (H2O2) with slight warming. The final step requires the addition of
hydrochloric acid (HCl) heated to the point of reflux without boiling.
The selective extractions, with the exception of the residual phase, were con-
ducted in 40-ml centrifuge tubes to minimize the loss of materials. Between each
successive extraction, supernatant separation was effected by centrifugation as de-
scribed in Section II.A. The Pb content in the supernatant was analyzed by AAS.
Four random duplicates were conducted.

III. RESULTS AND DISCUSSIONS

A. SOIL PROPERTIES

The soil properties reported in Table II with respect to CEC, S^, and soil pH
for the untreated soil, the soil with carbonates extracted, and soil with both car-
bonates and oxides removed present some interesting results. It is noted that the
measured CEC of the untreated soil is much higher than the CEC of the soil with
carbonates extracted. It is not immediately clear if this is due to the extraction of
the carbonates, and thus the loss of the CEC associated with the extracted carbon-
ates, or to the effects of the chemical procedure used to determine the CEC on eas-
ily solubilized carbonate minerals. Since the CEC of pure carbonates is minor to
insignificant, the latter explanation is preferred; however, the results obtained need
further evaluation. The S^ of the untreated soil is seen to be about 10% less than
the S^ of the soil with carbonates extracted. One could therefore speculate that the
removal of the residual carbonate bonding (Yong and Warkentin, 1975; Mitchell,
1976; Kersten and Forstner, 1989) provided the opportunity for greater particle
dispersion, thus providing for a larger S^. Further evaluation of this speculation is
needed in respect to the CEC of the two soils (untreated and carbonate removed).
The extraction of both the carbonates and the oxides resulted in a CEC which
was slightly greater than the CEC of the soil with carbonates extracted (Table II).
The implications of this have yet to be fully determined; however, the increase in
CEC is likely due to the loss of variable charge surface associated with the natur-
al soil amorphous oxides.
The reductive dissolution of oxides using the oxalic acid method could reduce
the "structural" iron in clay minerals such as smectites. Rozenson and Heller-Kallai,
as reported by Kersten and Forstner (1989), found that whereas the extractant cit-
rate-dithionite buffer will attack iron-rich layer silicates, no such problem has been
reported when oxalic acid extractant was used. Stucki et al. (1984) examined the
Pb and Cu Retention 137

reduction of structural iron in a citrate bicarbonate solution using Na^S^O^ as a re-

ductant and found that the structural iron was reoxidized by exposure to oxygenat-
ed water. Since the soil samples in this present study were washed three times with
distilled water and air dried after each extraction, this was not seen as a possible
complication. Furthermore, the CEC measurements did not increase after oxide ex-
traction to such an extent that would suggest structural Fe had been reduced.
It is useful to note that the decrease of the S^ of the soil with extraction of both
the carbonates and the oxides supports a previous experience reported by Yong et
al (1992a) for the same soil. In that particular instance, instead of extracting car-
bonates and oxides, iron and silica amorphous oxides were added to the soil such
that they made up 15% of the soil composition. The addition of these oxides re-
sulted in a 50 to 100% increase in the S^, depending on the proportions of silica
to iron oxide added. A similar increase was recorded in the CEC of the soil amor-
phous oxide mixture when measured at pH 7.

B. SOIL S U S P E N S I O N T E S T S

The results for the metal retention soil suspension tests for the untreated soil
without pH adjustment are shown in Figure 1. As can be seen, complete retention
of Pb and Cu is obtained by the untreated soil without pH adjustment for original
concentrations as high as 40 nmiol-L~ ^ for Pb and 50 mmol-L~ ^ for Cu. This com-
pares well with previous work performed by Yong and Phadungchewit (1993) for
the same soil.
The problem of distinguishing between retention by precipitation mechanisms
as opposed to retention by sorption is rendered difficult because of experimental
constraints. Soil suspension studies reported previously (Farrah and Pickering,
1977, 1978, 1979; Maguire et al, 1981; Yong et al, 1990; Yong and Sheremata,
1991; Yong and Phadungchewit, 1993) indicate that accumulation of heavy metal
contaminants increases with increasing pH, and that precipitation of the heavy met-
als at around neutral pH and above may result in the formation of compounds such
as carbonates, hydroxides, sulfates, and chlorates species. At acidic pH values,
heavy metals become mobile and may adsorb onto clay soil particles. However, ad-
sorption becomes less effective due to competition at the exchange sites from H"^
ions. The initial pH of the untreated soil used in this study was 8.2; however, the
equilibrium pH decreased with increasing initial metal concentration (Fig. 1). Dis-
tinguishing between adsorbed and precipitated Pb in the perceived "retention" of
Pb also depends on the concentration of Pb introduced into the soil suspension—
as shown previously by Yong (1996) for a kaolinite soil suspension in interaction
with Pb (Fig. 2). As noted in the diagram, some of the precipitated Pb was "record-
ed" as Pb adsorbed by the soil solids at pH values above approximately 6.5.
To investigate the possibility of Cu and Pb precipitation as a function of pH, to-
238 Yong and MacDonald

140

Initial Pb or Cu
Concentration (mmol L'^) 12.5 25 37.5 50 100 150
Final Pb Supernatant pH 8.2 7.5 7.2 6.9 6.7 5.4 4.8
Final Cu Supernatant pH 8.2 7.1 6.8 6.5 6.4 5.8 4.7

•H- •+- H- -4- -h

0 5 10 15 20 25 30
Final Supernatant Concentration (mmol L'^)
Figure 1 Single metal retention by untreated soil without pH adjustment.

pH
Figure 2 Pb partition in kaolinite suspension in relation to pH (Yong, 1996).
Ph and Cu Retention 239

tal metal concentration, and the presence of ligands, the USEPA geochemical mod-
el MINTEQA2 was used. Metal precipitation was investigated with and without the
presence of carbonates, assumed to be calcite (CaC03). To investigate the effect of
calcite, 0 0 3 " and Ca^"^ components were set at the same concentration as mea-
sured in the soil as carbonate content (Table I). Allison et al (1991) described that
in theory it does not affect the final result of the model as to whether the totals for
various components are specified as dissolved or as precipitated since MINTEQA2
will shift mass from the dissolved to the solid phase and vice versa as required for
equilibrium. Therefore the calcite was modeled by the inclusion of the separate dis-
solved components of Ca^"^ and C03~. The environment, with calcite or calcite-
forming components, provides the opportunity for the soluble Pb concentration to
be influenced and/or controlled by the precipitation of cerrusite (PbC03), as shown
in Table III. The removal of the soil calcite (modeled by excluding the calcite com-
ponents from the modeling process) reduces the amount of precipitation and
changes the controlling species from cerrusite to Pb(0H)2, as shown by Table III.
Soluble Cu precipitation in the same ion environment will be controlled by two
species, malachite (Cu2(OH)2C03) and azurite (Cu3(OH)2(C03)2), as shown in
Table IV. The removal of the calcite components from the modeling exercise re-
duced the precipitation of Cu but not to the same extent as Pb. Tenorite (CuO) be-
came the precipitate controlling Cu solubility when calcite was not present in the
system (Table IV).
The findings of the geochemical model suggest that precipitation may have
made a large contribution to the Pb and Cu retention measured when no pH ad-
justments were performed (Fig. 1) on the soil suspension.

Table III
Precipitation of Pb with and without the Presence of Calcite as Determined
by the USEPA Geochemical Model MINTEQA2 (Version 3.11)

Percentage of initial Pt> precipitated"^

as cennsite, with calcite present as Pb(OH)2, without calcite present

Initial Pb Equilibrium pH Equilibrium pH
concentration
(mmol-L~^) 4 5 6 4 5 6

0.5 0 92.6 99.4 0 0 98.9

5 53.2 99.2 99.9 0 0 98.5
12.5 76.4 99.6 100 0 0 97.8
25 82.0 99.7 100 0 0 95.7
50 74.7 97.4 99.7 0 0 66.8

"All Pb precipitation in the presence of calcite was as cerrusite (PbCOg), and all Pb precipitation with-
out calcite present was as PbCOH)^.
240 Yong and MacDonald

Table IV
Precipitation of Cu with and without the Presence of Calcite as Determined
by the USEPA Geochemical Model MINTEQA2 (Version 3.11)

Percentage of initial Cu precipitated"

as azurite and/or malachite as tenorite

with calcite present without calcite present
Initial Cu Equilibrium pH Equilibrium pH
concentration
(mmol-L"^) 4 5 6 4 5 6

0.5 0 0 92.9 M 0 0 90.4

5 0 80.5 A 99.3 M 0 0 98.8
12.5 0 91.8A 99.7 M 0 36.1 99.5
25 0 95.4 A 99.8 M 0 64.3 99.7
50 0 97.2 M/A 99.9 M 0 79.3 99.8

"^AU precipitation in the presence of calcite was as malachite (Cu2(OH)2C03) and/or azurite
(Cu3(OH)2(C03)2) as indicated by an M and/or A, respectively, adjacent to the percentage value. All
precipitation without calcite present was as tenorite (CuO).

The adjustment of initial soil suspension pH values to levels of approximately

5 and below resulted in an overall decrease in Pb and Cu retention by as much as
90% (Figs. 3,4, and 6) from the retention noted without initial soil pH adjustment
(Fig. 1). Figures 3 and 4 show the test results for the untreated and Pb-treated soil
suspensions for initial suspension pH values of 5.2 and 4.0, respectively. Results
from soil suspension tests performed at a constant initial Pb concentration of 5
mmol'L"^ but across a range of pH values are summarized in Figure 6. As can be
noted from Figures 3, 4, and 6, the effect of carbonate removal on the amount of
Pb retained is relatively minor. However, when the oxides were removed, it is seen
that the differences in retention of Pb are considerable, particularly for the condi-
tion when the initial soil suspension pH was 4.0 (Fig. 4) or at final pH values be-
low 4 (Fig. 6). Similar patterns of retention behavior have been observed for Cu
as the contaminant metal (Figs. 7 and 8).
The effect of removal of the carbonates from the soil can be considered to be
minimal for Pb at an initial soil solution pH of 5.2. However, a slight increase in
retention of Pb due to the removal of soil carbonates is apparent at an initial pH
of 4.0 (Figs. 3 and 4). At an initial Pb concentration of 5 mmol-L~^ a slight in-
crease in Pb retention upon the removal of soil carbonates at final pH values of
approximately 4 and below was observed. However, above a final pH of 4, the
soil carbonate extraction did not affect the overall quantity of Pb retained (Fig.
6). In almost all cases, final pH values, as shown in Figure 5, indicate a drop in
pH from the initial soil suspension pH levels. Generally, final pH values in the
 25

• Soil untreated

a Soil treated for carbonate extraction

o 20
o A Soil treated for carbonate and oxide extraction

o
I 15

10 +
o
o
Q.

10 15 20 25 30 35 45
Final Pb Concentration in Supernatant (mmol L'^)

Figure 3 Pb retention at an initial soil suspension pH of approximately 5.2 for untreated soil, soil
treated for carbonate extraction, and soil treated for carbonate and oxide extraction.

25

• Soil untreated

• Soil treated for carbonate extraction

o 20
A Soil treated for carbonate and oxide extraction

10 15 20 25 30 35 40 45
Final Pb Concentration in Supernatant (mmol L'^)

Figure 4 Pb retention at an initial soil suspension pH of approximately 4.0 for untreated soil, soil
treated for carbonate extraction, and soil treated for carbonate and oxide extraction.
242 Yong and MacDonald

5*^

^+ » !
:
(0 3 X
c
° • Soil untreated
° • Soil treated for carbonate extraction
2+
^ ^ Soil treated for carbonate and oxide extraction

1 + " * ^ Filled symbols - Initial pH of approx. 4.0.

°° ^ Open symbols - initial pH of approx. 5.2.

-h -h -h -f-
10 20 30 40 50
Added Initial Pb Concentration (mmol L'^)

Figure 5 Final pH values of Pb soil suspension tests performed at initial pH values of approximate-
ly 4.0 and 5.2.

5.0

- 4.6 +
(0 I
^5 4.0 +

? 3.5 +
^ I
E 3.0 +

.9 2.5 +

I 2.0 I
c
O I
O 1.5 +
Q. • Soil untreated
? 10 +
- I • Soil treated for carbonate extraction
0 0.5 +
A Soil treated for carbonate and oxide extraction
0.0 •+- •+- -h
-+•
5
Final pH

Figure 6 Pb fraction retained at an initial Pb concentration of 5 mmol-L ^ for untreated soil, soil
treated for carbonate extraction, and soil treated for carbonate and oxide extraction.
Pb and Cu Retention 243

soil suspensions which had an initial pH of 5.2 are above those with an initial soil
suspension of pH of 4.0. At higher final pH values, Pb interaction with the soil
carbonate results in its precipitation as cerrusite (Table III). However, as equilib-
rium pH values drop below 4.0, cerrusite precipitation decreases. Instead the soil
carbonates are dissolved, allowing the cation component of the soil carbonate to
compete with the Pb for adsorption. The removal of the soil carbonate phase and
the resulting decrease in competing cations could be an explanation for the ob-
served increase in Pb retention. A similar explanation could be considered for the
minor increases in Cu retention observed at initial pH values of 4.2 given the role
of soil carbonates in the precipitation of Cu as malachite and azurite. As was the
case for Pb suspension tests, final pH values for Cu suspension tests indicate a
drop in pH from the initial soil suspensions pH values (Fig. 9). The removal of
the soil carbonates resulted in a slight decrease in the retention of Cu at an initial
soil solution pH of 5.3 (Fig. 7). One could speculate that at an initial soil solution
pH of 5.3 some Cu precipitation may have occurred due to complexation with an-
ions liberated during the pH adjustment, forming Cu species of low solubility.
The removal of the carbonate phase, which is conducted using a pH 5 extractant,
may have removed the source of these anions, resulting in less Cu precipitation
and hence less retention.

ilU -

• Soil untreated
'L- 18 -
'o
(0
• Soil treated for carbonate extraction
o 16-
o A Soil treated for carbonate and oxide extraction
? 14- A

"o

i^-'
c
.9 10-
2
1 8-
c
o
^3 6-
o •
•§ 4 - _A / g ^ - ^
c
!2 __n
'/ ^sjfe: n
d = duplicates
0- ^T 1 1 1 +
10 20 30 40 50
Final Cu Concentration in Supernatant (mmol L'^)

Figure 7 Cu retention at an initial soil suspension pH of approximately 5.3 for untreated soil, soil
treated for carbonate extraction, and soil treated for carbonate and oxide extraction.
244 Yong and MacDonald

Changes in the mass ratios of soil components due to the removal of the soil
carbonates should also be considered as a possible explanation for observed re-
sults; i.e., the extraction of carbonates from the soil will result in a slight increase
in the clay minerals, oxides, and organic material present per gram of soil. Fur-
thermore, the resulting increased exposure of S^ (Table II) may have influenced
the retention when an increase has been observed.
A considerable increase in the retention of the two metals occurred with the re-
moval of amorphous oxides (Figs. 3, 4, and 6-8). As depicted by Figure 6, com-
plete retention of Pb on the untreated soil and the soil subjected to a carbonate ex-
traction is obtained only when final pH values have exceeded 6. However, the soil
that has undergone a carbonate and oxide extraction treatment retains over 90% of
the Pb at a final pH value as low as 3.5 and reaches almost complete retention of
Pb at pH values between 4 and 5. This set of results is expected inasmuch as simi-
lar observations have been made by other investigators; e.g., Elliot et al (1986)
found that when iron oxide was removed from the two clay soils used in their study,
adsorption of heavy metal cations increased. The authors attributed the increase to
two factors, the first being increased electrostatic attraction due to the reduction in
the zero point of charge (ZPC) of the soil, and the second being the stripping of
oxide coatings and oxides bound to structural exchange sites—thereby increasing
the accessibility of the heavy metal cations to these sites.

^u -
• Soil untreated
£? 18 •
s
o 16-
D Soil treated for carbonate extraction

o A Soil treated for carbonate and oxide extraction

5 14-
"o
1 12-
£^ A

c
.2 1 0 -

1
1 8- ^^^^'^''tr
o
c
O ^ ^ D
O 6-
3
o
" a D
? 4- / T
c 7/ _ ^ , . . — — " • "\ ' ^ • _ •
1 2-
11 1
}kzLm ^ d = duplicates
0- 1* ^ 1 -^ 1 h
10 20 30 40 50
Final Cu Concentration in Supernatant (mmol ' L'^)

Figure 8 Cu retention at an initial soil suspension pH of approximately 4.2 for untreated soil, soil
treated for carbonate extraction, and soil treated for carbonate and oxide extraction.
Pb and Cu Retention 245

6-

5 •fc
S
• n •
4 +• ! -
a

(0 3
c
° • Soil untreated
° • Soil treated for carbonate extraction
2+
^ ^ Soil treated for carbonate and oxide extraction

" * ^ Filled symbols - Initial pH of approx. 4.2.

1+
° ° ^ Open symbols - Initial pH of approx. 5.3.

-H -f- -h -H
10 20 30 40 50
Added Initial Cu Concentration (mmoles L'^)

Figure 9 Final pH values of Cu soil suspension tests performed at initial pH values of approximate-
ly 4.2 and 5.3.

It should be noted that not all reports on retention of the heavy metals upon re-
moval of amorphous oxides have shown increases in retention. For example, Cav-
allaro and McBride (1984a,b) have reported considerable reduction in Zn and Cu
sorption following the removal of the oxide fraction from an acid subsoil, and El-
liot and Liberati (1981) have also reported similar decreases in retention in their
studies on Cd adsorption on soils. It is likely that the manner in which the amor-
phous oxides are distributed within the system can affect their capability to retain
heavy metals. Yong and Ohtsubo (1987) and Ohtsubo et al. (1991) have shown
that the ambient pH of the system is not as important as the initial pH conditions
governing the contaminant-soil interaction process. Depending on the initial pH
conditions and ZPC of the oxides, the oxides can either coat the particles or coex-
ist as discrete particles at the ambient pH. Similar observations have been made
by EUiot et al (1986) with respect to the role of oxides in immobilizing metals.
In studies where the nature and form of mixed oxides have been examined in
relation to their ability to retain metals, Meng and Letterman (1993) demonstrat-
ed that Cd and Ca adsorption on mixed oxides was affected by the nature of the
oxide; e.g., adsorption by particles coated with A1(0H)3 was almost identical to
adsorption by A1(0H)3, and that SiO^ partially coated with Al(OH)3 showed en-
hanced adsorption. However, Cd adsorption on mixed SiO^ and Fe(OH)3 was
found to be the same as on a similar amount of pure Fe(0H)3. Meng and Letter-
man (1993) observed the mixed oxides by transmission electron microscopy and
found that unlike the Al(OH)3-Si02 mix, Fe(0H)3 formed as discrete precipitates.
246 Yong and MacDonald

As discussed under Material and Methods (Section II.B), the soil suspensions
were first adjusted to an initial pH condition, and then the metal solutions were
added at a pH of 4. Upon completion of the metal adsorption stage, the equilib-
rium pH of the system was measured, and as expected, in most cases the pH val-
ues had dropped below the initial pH of the soil suspension (Figs. 5 and 9). Equi-
librium pH values ranged from close to the initial soil suspension at low initial
metal concentrations to pH values of 3.2 at high initial metal concentrations. The
pH drop could be a result of many reactions in the system, including but not Hm-
ited to hydrogen ions released due to metal-proton exchange reactions on surface
sites, hydrolysis of metals in the soil solution, precipitation of metals, and the ad-
dition of pH 4 metal solution. In Figures 10 and 11, the metal ions retained are
compared to the H"^ released for soil suspension tests performed on the soil with
carbonates and oxides extracted. The ratio of hydrogen ions released to Pb ions
retained averaged 0.7 for both initial pH conditions but started out low (0.2 to 0.3)
at initial Pb concentrations below 10 mmol-L~\ reaching approximately 1.0 at
concentrations of 25 mmol-L~^ and above. The ratio of hydrogen ions released
to Cu ions retained averaged 2.5 for Cu at an initial pH of 4.2 and 1.5 at an ini-
tial pH of 5.3. In both cases, more hydrogen ions were released than Cu ions re-
tained. Without further information it is not possible to determine the reactions

lO •

I
o
(0

^14- • I
o
o a 1
"• 1 2 - D
o
E •
£10-
A
A
CO
§ 8- • Pb retained (initial pH 4.0)
o
a:
^ 6 • • H released (initial pH 4.0)

1
'§ 4-
•
A Pb retained (initial pH 5.2)

1
i. 2- * A H released (initial pH 5.2)
D
A
Q

0- A
A
_| •H 1 1 -1
10 20 30 40 50
Added Initial Pb Concentration (mmol L'^)

Figure 10 Pb retained and H released in soil suspension tests performed on the soil treated for car-
bonate and oxide extraction at initial soil suspension pH values of approximately 5.2 and 4.0.
Pb and Cu Retention 247

lO •

"5
(0

D
o
o a
'J- 1 2 - J
o I
E
^10- A 1
-a A A
o A
u>
OS o •
<D 8 - A
• Cu retained (initial pH 4.2)
A.
D •
D H released (initial pH 4.2)
c
'B 4- • A Cu retained (initial pH 5.3)
DC d A

d 2- A H released (initial pH 5.3)

0- i * H ' H 1 1—
10 20 30 40 50
Added Initial Cu Concentration (mmol L'^)

Figure 11 Cu retained and H released in soil suspension tests performed on the soil treated for car-
bonate and oxide extraction at initial soil suspension pH values of approximately 5.3 and 4.2.

(surface or solution) resulting in release of hydrogen ions and the corresponding

change in pH, although these ratios could be used to predict surface adsorption
reactions. When modeling on a microscopic scale by the use of surface com-
plexation models, the relationship between metal adsorption and proton release
is defined through the proposed reactions. However, in complex heterogeneous
systems, it is often necessary to study the system on a macroscopic scale. In such
systems the net proton release or consumption is due to all the chemical reactions
involving proton transfer. It is not possible to determine the source of the protons
other than the generic relationship between adsorption and proton activity (Hon-
eyman and Leckie, 1986).
By comparing the Pb and Cu mineral precipitation to the equilibrium activity
and final pH of the metals in supernatant of the suspension tests performed using
the soil with the carbonates and oxides extracted (Fig. 12), it can be seen that the
metal activities were below the saturation point of the most insoluble metal pre-
cipitates. This could be used as evidence in support of the hypothesis that adsorp-
tion and not precipitation is the dominant mechanism responsible for retaining the
metals on the soil with the oxides and carbonates extracted. To calculate activity
coefficients using the Davies equation, it was assumed that the extraction of the
carbonates and oxides had removed the soluble soil components which may affect
248 Yong and MacDonald

101
Approximate solubility limit of
10° Pb as Cerrusite (PbCOs) or
Pb(0H)2
101 ±
Approximate solubility limit
of Cu as Tenorite (CuO)
f 10-2

? 10-3 4.
IS
p 10^ +

E 10-5 -h

10^ I • Pb (initial pH of approx. 4.0)

• Pb (initial pH of approx. 5.2)
10-7 _|_
A Cu (initial pH of approx. 4.2)
A Cu (initial pH of approx. 5.3)
10^ H 1 1 1—
4 5 6
Final pH

Figure 12 Final pH versus equilibrium metal activity of Pb and Cu in the supernatant of soil sus-
pension tests performed using the soil treated for carbonate and oxide extraction with a comparison to
possible mineral precipitates.

the ionic strength of the soil solution. This assumption could not be appHed to the
soil suspension tests performed without the carbonates and oxides extracted since
the pH adjustments may dissolve some of these soil components, thus affecting the
ionic strength of the soil solution. Hence, similar calculations could not be made
for these soil suspension tests.

C. SEQUENTIAL EXTRACTION T E S T S

The distribution of Pb among soil components was examined using a sequen-

tial extraction procedure (Section II.C). Sequential extraction was performed on
eight samples of the soil taken from the suspension tests performed at variable pH
values but at a constant initial Pb concentration of 5 mmol-L~^ The distribution
determined, as shown in Figure 13, is compared to the additional retention ob-
tained when the carbonate and oxide components were extracted from the soil. At
equilibrium pH values of 4 and less, the exchangeable and carbonate phases both
played dominate roles in the retention of Pb. However, as the final pH increased,
the carbonate fraction become the dominate contributor to Pb retention, with the
Ph and Cu Retention 249

oxide component also increasing its contribution while the exchangeable fraction
became less predominant. No detectable Pb was found associated with the natur-
al soil organic material. It is difficult to correlate these operationally defined frac-
tions, extracted after contamination, to those components extracted from the soil
prior to contamination. For example, Pb extracted with the exchangeable fraction
could be associated with the clay minerals, oxides, natural organic matter, and even
perhaps carbonate components (Stumm and Morgan, 1996). Furthermore, Pb may
precipitate as a hydroxide and Cu as an oxide (Tables III and IV), which may not
necessarily be the result of interactions with natural soil oxides, although these pre-
cipitates may be extracted with the oxide extraction technique used. As can be seen
from Figure 13, both the carbonate and the oxide components play a major role in
retaining the Pb. However, when these two components are extracted from the soil
prior to addition of the Pb, the overall retention of Pb increases, as shown in Fig-
ure 6 and compared to the extraction results in Figure 13. This increase in reten-
tion is only apparent at final pH values below 5, since near complete retention of
Pb by all soils (treated and untreated) occurs above equilibrium pH values of 5.
These findings indicate that more research is required to understand the relation-
ship between postsorption sequential extraction of soil fractions to presorption ex-
traction of soil components.

6.0

8 5.0 +
o

r 4.0 +
o
E • Extracted from exchangeable
£3.0 fractions
• Extracted from carbonate and
exchangeable fractions
B
(D A Extracted from oxide, carbonate
0:2.0 and exchangeable fractions
X Extracted from residual, oxide,
o carbonate^ and exchangeable
2 1.0 fractions
><
UJ • Retention on soil treated for oxide
d = duplicates and carbonate extraction
0.0

Final pH

Figure 13 Sequential extraction of Pb from untreated soil added at an initial concentration of 5

mmol-L~i and compared to the Pb retention on soil treated for carbonate and oxide extraction.
250 Yong and MacDonald

IV. CONCLUDING REMARKS

The soil properties reported for the untreated and treated soils presented some
interesting but inconclusive results. Speculation on the decrease in the CEC with
carbonate extraction evokes two possible explanations. The loss of the CEC asso-
ciated with the extracted carbonates could result in a decrease in the overall CEC
of the soil; however, the CEC of pure carbonates is minor to insignificant. The pre-
ferred explanation is that the decrease is due to the effects of the chemical proce-
dure used to determine CEC on easily solubilized carbonate minerals. A similar
reduction in S^ upon carbonate extraction could be due to greater particle disper-
sion caused by the removal of the residual carbonate bonds. The extraction of both
the carbonates and the oxides resulted in a CEC slightly higher than that measured
with just the soil carbonates extracted. The implications of this have yet to be ful-
ly determined. However, it is speculated that the increase in the CEC is likely due
to the loss of variable charge surfaces associated with the soil amorphous oxides.
Without pH adjustment the untreated soil retains high concentrations of Pb and
Cu; however, when initial soil suspension pH values were adjusted to 5 and less,
metal retention decreased by as much as 90%. Analysis of Pb and Cu precipitation
in the presence of calcite using the USEPA geochemical model MINTEQA2 indi-
cates that much of this retention at unadjusted pH levels could be the result of pre-
cipitation.
The effect of removal of the carbonates from the soil can be considered to be
minimal for an initial soil solution pH of approximately 5; however, a slight in-
crease in retention of Pb and Cu was observed at initial soil solution pH values of
approximately 4 and final pH values of 4 and below. The removal of the soil car-
bonate phase and the resulting decrease in competing cations associated with soil
carbonates at low pH values could be an explanation for the observed increase in
retention. The extraction of soil carbonates and oxides increased the retention of
Pb by approximately threefold and doubled the Cu retention. This could be attrib-
uted to two factors, the first being increased electrostatic attraction due to the re-
duction in the variable charge sites on the soil surface, and second being the strip-
ping of oxide coatings and oxides bound to structural exchange sites—thereby
increasing the accessibility of the heavy metal cations to these sites. However, at
this point these explanations are speculative and further research is required to de-
termine the exact cause(s).
Upon completion of the metal adsorption stage the equilibrium pH of the sys-
tem had dropped below the initial pH of the soil suspension. The pH drop could
be a result of many reactions in the system (surface and solution), and for that rea-
son, it is not conclusive evidence that adsorption has occurred. However, evidence
in support of the hypothesis that adsorption and not precipitation is the dominant
mechanism responsible for retaining the metals on the soil with the oxides and car-
bonates extracted is obtained by comparing the Pb and Cu mineral precipitation to
Pb and Cu Retention 251

the equilibrium activity and final pH of the metals in supernatant. For these soil
suspension tests, the metal activities were far below the saturation point of the most
insoluble metal precipitates.
Sequential extraction analysis determined that the Pb retained on the untreated
soil from an initial concentration of 5 mmol-L~^ was associated predominantly
with the carbonate component—with exchangeable and oxide soil components
also retaining significant quantities. However, the extraction of the carbonate and
oxide components prior to addition of the Pb resulted in an increase in retention.
Such findings indicate that more research is required to understand the correlation,
if any, between postsorption sequential extraction of soil components to presorp-
tion extraction of soil components. Continuing study with selective sequential ex-
traction tests, similar to the ones performed in this study, will be conducted with
the contaminated samples obtained using the procedures described heretofore.

ACKNOWLEDGMENTS
The authors are grateful for helpful comments and suggestions offered by three anonymous re-
viewers. Furthermore, a special thanks is expressed to Dr. E. A. Jenne for his editorial conmients and
manuscript preparation guidance. The authors wish to record their appreciation to the Natural Sciences
and Engineering Research Council of Canada (NSERC) for Grant in Aid of Research A-882, which
provided the financial support for studies conducted.

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