S I M U L T A N E O U S S O R P T I O N OF Cd, Cu, Ni, Zn, Pb, AND Cr ON SOILS

TREATED WITH SEWAGE S L U D G E SUPERNATANT

SUDUAN GAO I, WILLIAM J. WALKER 2, RANDY A. DAHLGREN I * and

JEFF BOLD ~
Department of Land, Air and Water Resources, UniversiO, of California at Davis, CA 95616;
~-SEACOR International, Inc. Sacramento, CA 95814, 3 Dames and Moore. Sacramento, CA 95826

(Received 29 March, 1995; accepted I December, 1995)

Abstract. Disposal of sewage sludge creates the potential for heavy metal accumulation in the
environment. This study assessed nine soils currently used as Dedicated Land Disposal units (DLDs)
for treatment and disposal of nmnicipal sewage sludge in the vicinity of Sacramento, California.
Adsorption characteristics of these soils for Cd, Cu, Ni, Zn, Pb, and Cr were studied by simultaneously
mixing these elements in the range of 0-50 izmol L -I with sludge supernatant and reacting with
the soil using a soil:supematant ratio of 1:30, pH = 4.5 or 6.5, and constant ionic strength (0.01 M
Na-acetate). The concentration of metals in the supernatant was determined after a 24 hr equilibration
period. Adsorption isotherms showed that metal sorption was linearly related to its concentration in the
supernatant solution. The distribution coefficient Kd (Ka = concentration on solid phase/concentration
in solution phase) was computed as the slope of the sorption isotherm. The distribution coefficients
were significantly correlated to soil organic matter content for Ni, Cu, Cd, and Pb at pH 4.5 and for
Ni, Cu, Zn, and Cd at pH 6.5. There was also a correlation between K~t and soil specific surface
area but no relationship to other soil properties such as CEC, clay content, and noncrystalline Fe
and AI materials. Therefore, soil organic carbon and surface area appear to be the most important
soil properties influencing metal adsorption through formation of organo-metal complexes. The Ka
values for all elements were higher at pH 6.5 than at 4.5. Selectivity between metals resulted in
the following metal affinities based on their Ka values: P b > C u > Z n > N i > C d ~ C r at pH 4.5 and
P b > C u ~ Z n > C d > N i > C r at pH 6.5.

Key words: metal sorption, sewage sludge, sorption isotherms, competitive sorption, organo-metal
complexes

1. Introduction

Land disposal of sewage sludge may result in leaching of heavy metals from the
sludge and the soil into surface and ground waters. The potential environmental
risk from metal contamination associated with disposal of sewage sludge depends,
in part, on the metal sorption characteristics of the soils which are a function of the
soil physio-chemical properties.
In order to assess and predict the ability of the Dedicated Land Disposal units
(DLDs), employed by Sacramento Regional County Sanitation District, to act as a
zone of metal attenuation, the partitioning of metals between the solid phase and
solution phase was determined. Components that partition more strongly to the
solid phase exibit low mobility in soils while those that partition more strongly to

" Corresponding author.

Water; Air, and Soil Pollution 93: 331-345, 1997.

(~) 1997 Kluwer Academic Publishers. Printed in the NetherlandY.
332 SUDUAN G A O E T A L .

the liquid phase have greater mobility and may ultimately contaminate the ground
water.
The transport and mobility of heavy metals in soil depend on concentration,
speciation and solubility. The solubility of heavy metals in soil is controlled by
reactions with solid phases. Once sewage sludge is applied to soil, the heavy metal
species undergo several possible fates including: adsorption/desorption reactions,
precipitation/dissolution reactions, plant uptake, and possible transport through the
soil profile. Accumulation of heavy metals in surface soils has been reported from
sewage sludge application (Chang et al., 1983; Sposito et al., 1982; Behel et al.,
1983).
Complexation of metals by organic ligands is one of the mechanisms control-
ling the availability and mobility of metals. Formation of soluble organo-metal
complexes increases availability and mobility of trace metals (Sposito et al., 1982:
Elliott and Denneny, 1982; Chairidchai and Ritchie, 1990). On the other hand, for-
mation of metal complexes with solid-phase organics may increase the partitioning
of metals toward the solid-phase. Therefore, organic matter may be an important
lector influencing the retention of trace metals by soils.
Stability of complexes varies among metals and among organic ligands for the
same metal. Copper forms a relatively strong 1:1 complex (log K = 3.9) with acidic
functional groups in fulvic acid extracted from sewage sludge (Sposito et al., 1979).
Complexation of Cu by the carboxylate group of humic acid results in formation
of a unidentate complex (i.e., a single M-O bond) (Boyd et al., 1981). Cadmium
complexation with organic ligands is much weaker than that for Cu (Inskeep and
Baham, 1983). Measured and estimated stability constants of divalent metals with
fulvic acid extracted from sewage sludge for Ni, Cu, Zn, Cd, and Pb are 3.81,3.88,
3.54, 3.04, and 4.22 (log K), respectively, for 1:1 strong complexes and 2.08, 2.11,
1.74, 2.27, and 2.62 (log K), respectively, for a weaker set of complexes (Sposito et
a/., 1979; 1981). These published values predict a stability trend for organo-metal
complexes of P b > C u > N i > Z n > C d .
Sorption affinities of metals to solid-phase surfaces are very different among
metals which is reflected by the sorption maxima and competition among ions.
Copper adsorption was not significantly affected by Zn additions up to 250 tL.g
mL -I, although the presence of Cu even at a concentration of 15 tl.g mL -1 com-
pletely prevented Zn sorption in one soil (Kurdi and Doner, 1983). Sorption of
Cu, Ni, and Co occurred in the order of C u > N i ~ C o in a Ca-saturated soil (Hatter,
1992). Copper caused a significant decrease in Ni sorption, but Cu sorption was not
affected by Ni. It was concluded that Ni was retained by an exchange mechanism,
but Co and Cu sorption was more complex (Harter, 1992). Addition of Ni or Cu
only affected Zn adsorption when metal concentrations in solution were in excess
of the soil sorption capacity (Elrashidi and O ' C o n n o r , 1982). A study by Kuo and
Baker (1980) showed that a combination of Cu and Cd caused a decrease in Zn
adsorption only at p h i 6 . 5 . Copper sorption was decreased by the presence of Zn
and Cd at p H i 5 to 6 and Cd sorption was decreased at all pH values. All previous
 SIMULTANEOUS SORPTION OF Cd, Cu, Ni, Zn, Pb, AND Cr ON SOILS 333

studies examining sorption mechanisms and competition of ions were restricted to

two or three metals. However, multiple metals are present in sewage sludge and
sorption studies simulating the natural composition of sewage sludge are necessary.
In this study, we simulate metal adsorption characteristics under close to natural
conditions by using sludge supernatant as the background solution and by simul-
taneously adding Cd, Cu, Ni, Zn, Pb and Cr to the supernatant. The supernatant
was obtained from a sludge storage basin containing salts, trace elements, and
dissolved organic carbon. By simultaneously spiking the supernatant with these
elements, adsorption capacities of soils for these elements were measured under
realistic environmental conditions.
The objective of this study was to determine the adsorption characteristics of
contrasting DLD soils for metals commonly encountered in municipal sludge (Cr,
Ni, Cu, Zn, Cd, and Pb). Simultaneous metal sorption isotherms, the relationship
of soil physio-chemical properties to sorption parameters, and pH effects on metal
adsorption were examined.

2. Materials and Methods

2.1. SOILS

Soils were collected from DLDs, employed by Sacramento Regional County San-
itation District for disposal of municipal sewage sludge. Nine representative soil
samples were chosen to examine the range of soil properties in the proposed disposal
area. The following properties were determined: CEC by ammonium acetate (pH =
7) extraction (Soil Survey Staff, 1984), pH (1:1 soil:solution) following a 15 min
equilibrium period, mineralogy by X-ray diffraction (Whittig and Allardice, 1986),
noncrystalline A1 and Fe materials by acid oxalate (McKeague, 1976), secondary
iron oxides and hydroxides by the citrate-dithionite extraction (Holmgren, 1967),
organic carbon by dry combustion (Nelson et al., 1982), particle size fractionion
by pipette method (Gee and Bauder, 1986) and surface area by the EGME method
(Carter et al., 1982). It must be pointed out that the use of the EGME method for
estimating surface area is not without limitations and assumptions (Carter et al.,
1982). For example, the EGME method is generally accepted for clay samples:
however EGME may have a strong attraction for organic matter, resulting in an
over estimation of surface area for organic-rich soils.

2.2. SLUDGE SUPERNATANT PREPARATION

A representative sludge supernatant was obtained from a sludge storage basin,

filtered through a 0.22 #m membrane filter and stored at 3 ~ prior to use. The
ionic strength and pH were buffered with 10-2 M Na-acetate. Stock solutions of
CrO]-, Ni :+ , Cu 2+, Zn 2+, Cd e+ , and Pb :+ were diluted into the sludge supernatant
to obtain equal molar metal concentrations of 0, 2, 5, 10, 20 and 50 H.mol L I
334 SUDUAN GAOETAL.

The final pH (4.5 or 6.5) of each treatment was checked and adjusted if necessary
with HC1 or NaOH. The G E O C H E M chemical equilibrium program (Sposito and
Mattigod, 1979) was used to verify that all metals were undersaturated in the initial
solutions.

2.3. A D S O R P T I O N EXPERIMENT

Thirty mL o f p H buffered sludge supernatant containing a given metal concentration

was added to I g of soil ( < 2 mm fraction) in a 50 mL Oakridge centrifuge tube
(polyethylene). The tubes were shaken for 24 hr on a horizontal reciprocating
shaker and then centrifuged at 17 210 RCF for 10 min. A preliminary study
showed that metal sorption equilibrium was reached within 24 hr. The supernatant
was collected, filtered (0.22 t*m membrane filter), and analyzed for Cr, Ni, Cu,
Zn, Cd, and Pb using an Inductively Coupled Argon Plasma-Mass Spectrometer
(Model ELAN 500, manufactured by Perkin Elmer-Sciex). Rhodium was used as
an internal standard. The detection limits for Cr, Ni, Cu, Zn, Cd, and Pb were
3.8x10-4,5.1x10-4,7.9x10 4,1.2xl0-3,6.2xl0-4, and2.4xl0-4H.molL-i '
respectively. Duplicate analyses were conducted for all treatments.

2.4. DATA ANALYSIS

The concentration of Cr, Cd, Ni, Cu, Zn, and Pb sorbed to the solid phase was
calculated as the difference between the concentration added and the concentration
in solution at equilibrium. The distribution coefficient (K,~) for each element was
calculated from the following formula:

K~z = Ci (solid phase)/Ci (solution phase)

where C represents the concentration of element i. If the concentration adsorbed

on the solid phase is linearly correlated to the concentration in the solution phase,
the slope of the plot (Ci on solid phase vs Ci in solution phase) is the Kd value
for the soil. This was the case for most metals over the range of concentrations
in this study. The correlation between the distribution coefficients and selected
soil physio-chemical properties was tested to determine if significant relationships
occurred between soil properties and the adsorption of metals.

3. Results

3.1 . S O I L AND SLUDGE SUPERNATANT CHARACTERIZATION

Selected chenaical and physical properties of the soils used in this study are shown
in Table I. The soils have a pH range of 5.6 to 8.4, organic carbon of 2.2 to 22.7 g
C kg 1, clay content of 10 to 58%, surface area of 89 to 164 m 2 g-I soil, CEC
 K
Table I
Selected chemical and physical properties of soils
Z
Surface Oxalate CBD
Soil Depth pH OC Particle-size area CEC Mineralogy ~ extracteable extractable
Sand Silt Clay smec/verm kaolinite mica Fe A1 Fe AI

(cm) (gkg-J) __(%) _ _ (m e g - I ) (cmol(+)kg -j) - - (g kg -I ) _ _ Z

9
TPI9 152-183 7.5 5.5 28 30 42 88.8 29.0 + ++ ++ 3.1 1.7 21.5 3.1
TP21 183-214 7.9 2.6 15 26 58 112.3 22.0 +++ + + 0.6 1.4 10.2 1.8
TP2I 244-274 7.6 22.7 20 43 37 164.7 29.2 +++ + + 1.7 2.3 6.4 1.8
TP22B 61-76 5.6 5.1 26 28 47 93.2 22.6 7
+++ - + 3.5 1.9 20.4 3.2 2-"
TP24 15-76 7.3 10.8 30 30 40 101.6 25.7 NO
+++ ++ + 1.0 1.1 9.1 1.8
TP24 122-152 7.2 2.2 26 64 10 109.4 24.2 +++ ++ + 2.7 1.9 8.1 2.9
TP26 122-152 8.4 19.9 16 29 55 119.5 27.1 +++ + + 0.3 1.1 3.9 1.3 >
z
TP27 61-91 6.9 2.6 28 22 50 106.4 21.5 +++ + + 1.5 1.5 20.2 2.8
TP28 61-9I 8.3 6.4 18 30 52 106.2 30.1 +++ ++ + 2.7 2.2 12.8 3.1
o
z
+++ Major; ++ Minor; + Trace; None detected.
r""

',..,O
336 SUDUAN GAO ET AL.

Table II
Composition of sludge supernatant

Component Concentration

pH 8.1

Solutes (imaol L -I
Na 3430
NH4 7189
K 711
Mg 558
Ca 820
CI 1636
NO3 739
PO4 1088
SO4 635

Cr 0.06
Ni 0.30
Cu 0.19
Zn 0.57
Cd 0.01
Pb 0.05

DOC 5162

of 21.5 to 29.2 cmol(+) k g - ~, low concentrations of noncrystalline Fe and A1, and

variable concentrations of secondary iron (6.4-21.5 g kg- 1). Most of the soils were
dominated with smectite/vermiculite clay minerals except for TP19 152-183 cm
which was dominated by kaolinite and mica.
The composition of the sewage sludge supernatant used in this study is provided
in Table II. Nitrogen and phosphorus are the dominant dissolved nutrients in the
supernatant. Dissolved organic carbon in the supernatant was 5162 #mol C L-I
The background concentrations of metals were low in this supernatant, less than
1 Hmol L -1. These values are negligible compared to the amount added in this
study.

3.2. ADSORPTION ISOTHERM AND K d

Adsorption isotherms for each element were determined by plotting x/m versus
C,,, where x/m represents the concentration of metal adsorbed in #mol g-I soil
while Ce represents the metal concentration in the solution phase at equilibrium
in Hmol L - l . All the plots showed the same pattern at both pH 4.5 and pH 6.5
with x/m linearly related to Ce. All the correlation coefficients for linearity were
 SIMULTANEOUS SORPTION OF Cd, Cu, Ni, Zn, Pb, AND Cr ON SOILS 337

0.8
Cr
~0.6-
o:
1o Ni
~:u.0:4-

~0.2-
~ 0.4
x 0.2
0 0 , ,,[ ....
5 10 15 20 25 30 35 0 5 10 15 20 25
Ce (p.mol/L) Ce (p.mol/L)

.~1.2
o
1.6

E=.0.8
E
"~ 0.4
Cu
0.8

~
o.6
1
1

0.4
0.2

~'''[ .... L .... i'''*l .... I .... I .... 0 ''1 ....

0 1 2 3 4 5 6 7 0 5 10 15 20 25
Ce (lamol/L) Ce (lamol/L)
0.6 1.6

Cd
..~ 0.4-
o
E
~ 0.8-
E 0.2-
X ~'0.4-

0
0 5 10 15 20 25 30 35 0 0.2 0.4 0.6 0.8 1 1.2
Ce (u.mol/L) Ce (p.mol/L)

/-'/gum 1. Representative adsorption isotherms for soils in this study. Isotherms are for TP-22B at
pH 4.5.

r>0.9 (p<0.01). Representative examples of adsorption isotherms are shown in

Figure 1 for soil TP22B 61-76 cm. Table llI shows the distribution coefficients for
all treatments.
Since the isotherms are linear, the distribution coefficient (Kd) can be deter-
mined as the slope of the isotherm line. The computed K(z values are provided in
Table Ill. There is great variation in the magnitude of Kd values among metals
within a given soil and among soils for a given metal. Comparison of K,zs for all
338 SUDUAN GAO ET AL.

Table III
Distribution coefficient Kd (L g-~) for nine representative soils proposed as
DLD sites

Soil Cr Ni Cu Zn Cd Pb

pH = 4.5

TP19 152-183 0.031 0.053 0.390 0.070 0.010 1.460

TP21 183-214 0.021 0.048 0.262 0.092 0.009 1.313
TP21 244-274 0.134 0.222 3.951 0.235 0.207 4.767
TP22B 61-76 0.018 0.040 0.208 0.034 0.014 1.242
TP24 15-76 0.015 0.050 0.869 0.758 0.093 4.070
TP24 122-152 0.026 0.047 0.322 0.063 0.009 1.467
TP26 122-152 0.018 0.080 1.322 1.359 0.171 4.059
TP27 61-91 0.019 0.038 0.274 0.072 0.017 0.753
TP28 61-91 0.023 0.070 0.917 0. I l l 0.026 1.922

pH = 6.5

TPI9 152-183 0.047 0.107 0.649 0.608 0.187 6.304

TP21 183-214 0.031 0.081 0.612 0.589 0.089 4.948
TP21 244-274 0.060 0.735 2.676 1.981 0.972 1.841
TP22B 61-76 0.035 0.109 0.965 0.585 0.132 1.399
TP24 15-76 0.038 0.132 0.916 1.114 0.206 9.663
TP24 122-152 0.035 0.095 0.935 0.652 0.116 11.508
TP26 122-152 0.028 0.186 0.983 2.896 0.433 1.312
TP27 61-91 0.035 0.081 0.777 0.425 0.102 10.971
TP28 61-91 0.028 0.230 1.399 1.448 0.271 14.280

soils showed the following affinity trend: P b > C u > Z n > N i > C d ~ C r at pH 4.5 and
P b > C u , - ~ Z n > C d > N i > C r at pH 6.5. It can be generalized that Pb has the highest
K~ values, followed by Cu and Zn, and then Cd, Ni, and Cr. The Ka values for soil
TP21 244-274 cm and soil TP26 122-152 cm are high for all the metals and both
soils have high organic carbon concentrations and surface areas (Table I).

3.3. CORRELATION BETWEEN K d AND SOIL PROPERTIES

The Kd represents the sorption affinity of metals for the solid phase. The corre-
lation between Kd values and selected soil chemical and physical properties was
examined. The significance of linearity between soil property and distribution coef-
ficient is shown in Table IV. Most element sorption was linearly related to organic
carbon concentrations and solid phase surface area at both pH 4.5 and 6.5. The
Kd values were not significantly correlated to soil organic carbon for Cr at either
pH 4.5 or 6.5, Zn at pH 4.5, and Pb at pH 6.5. There was no significant correlation
(p<0.05) between Kd and CEC, clay content, and noncrystalline forms of Fe and
 SIMULTANEOUS SORPTION OF Cd, Cu, Ni, Zn, Pb, AND Cr ON SOILS 339
Table IV
Signilicance of linear correlation coefficients (r) between soil properties and distribution coeflicient
(Ka)

Soil Organic Surface Non-crystalline Crystalline

property C area CEC Clay Fe AI Fe AI

pH 4.5

Cr 0.64 0.88** 0.37 -0.21 0.01 0.58 -0.31 -0.25

Ni 0.80** 0.94** 0.55 -0.09 -0.14 0.49 -0.47 -0.40
Cu 0.86** 0.93** 0.54 -0.24 -0.21 0.40 0.52 -0.48
Zn 0.66 (/.42 (}.57 ~0.23 J,).65 ~).65 ~).61 ~0.75"
Cd 0.98** 0.80* 0.60 0.06 q).49 -0.04 -0.68* -0.74*
Pb 0.93** 0.68* 0.4[ 4).02 -0.48 -0.1 I -0.73* -0.75*

pH 6.5

Cr 0.45 0.56** 0.44 ~).33 0.19 0.43 0.02 -0.06

Ni 0.77* 0.91 ** 0.54 q). 10 0.08 0.55 0.42 -0.34
Cu 0.71 * 0.87** 0.56 -0.16 0.02 0.64 -0.41 -0.23
Zn 0.89** 0.57 0.21 0.21 ~0.47 -0.10 -0.71 * -C).66
Cd 0.89** 0.90** 0.46 q).04 -0.18 0.40 -0.50 -0.46
Pb . . .. . .. . .. . .. . .. . . . .. . .

* I).05. ** 0.01 signiticance levels. " Not evaluated due to low Pb concentrations in solution phase.

Table V
Mean and standard deviation for sorption of metals by
tile nine soils when 50 Hmol L-I of each element was
added to shldge eftluent

pH 4.5 pH 0.5
Element (% adsorbed} (% adsorbed}
Ave. Std. dev. Ave. Std. dev.

Cr 41.9 5.3 51.8 5.3

Ni 65.2 9.7 81.5 7.1
Cu 92.5 5.7 97.0 (}.9
Zn 76.5 14.6 96.5 1.7
Cd 46.9 26.9 85.4 7.6
Pb 98.4 1.0 99.6 (/.4

AI. T h e r e w e r e a f e w c a s e s w h e r e t h e a m o u n t o f c r y s t a l l i n e F e o r A1 s h o w e d i n v e r s e
correlations to K~t ( p < 0 . 0 5 ) e s p e c i a l l y at l o w pH.
340 SUDUAN GAO ET A L

2
t a. pH=4.5 9 Cr
-I 9 Ni
1.5 t o 9 Ct,

~=. 1 [] Cc
E" o Pb

0 * 9
0 5 10 15 20 25 30 35
Ce (pmol/L)

2
9 Cr
t b. pH =6.5 9 Ni
1.5-~ 9 9 Cu
9 Zn
[] Cd
"I

o Pb

0.5

0 I . . . . I . . . . I . . . . I ' ' '

0 5 10 15 20 25 30 35
Ce (tamol/L)
Fi~,me 2. Adsorption usotherms for soil TP-22B at (a) pH = 4.5 and (b) pH = 6.5.

3.4. pH EFFECTS ON METAL SORPTION

At all concentrations, adsorption was greater at pH 6.5 than at pH 4.5. Tile effect
of pH on sorption of these elements is shown in Figure 2, Table III, and Table VI.
Figure 2 shows adsorption isotherms for soil TP22B at pH 4.5 and 6.5. Table III
shows that K,l values are generally higher at pH 6.5 than at pH 4.5 with few
exceptions. Table V shows the mean percentage of elements partitioned into the
solid phase of the nine soils. Chromate was the least adsorbed on the solid phase
 SIMULTANEOUS SORPTION OF Cd, Cu, Ni, Zn, Pb, AND Cr ON SOILS 341

~tnd showed non-linearity at high concentrations. The adsorption of chromate did

~ot change as significantly as other metals with pH changes. This is due to its
oxyanion characteristics in oxidizing conditions, and the adsorption mechanisms
are very different compared to that of positively charged metals. These results
confirm that adsorption for most metal cations increases as pH increases; however,
crystalline Fe or A1 do not contribute to retention of these metals. The positive
correlation between adsorption and organic matter content will be discussed in
more detail. The positive correlation between adsorption and surface area may be
a consequence of surface area being associated with the organic matter content
(Table II).

4. Discussion

The adsorption isotherms for metals in the concentration range 0-50 #mol L-I
displayed a linear relationship between the amount adsorbed and the concentration
in solution. The linear relationship may be due to the low range of metal concentra-
tions used in this study. Kurdi and Doner (1983) found that zinc and copper sorption
isotherms could be described by a linear Langmuir equation at low concentrations
whereas a Freundlich equation was necessary at high concentrations.
A significant correlation between the distribution coefficient (Kd) and soil organ-
ic matter was found for the metals Ni, Cd, Cu, and Pb at pH 4.5 and Ni, Cd, Cu,
and Zn at pH 6.5. The correlation between soil organic matter and the sorption
of the metals may be explained by formation of organo-metal complexes. To esti-
mate the stability of organic complexes with metals and the contribution of metal
partitioning between solid and solution, MINTEQA2 (Allison et al., 1991) was
used to speciate the metals at pH 4.5 and 6.5. The program was used to estimate
formation of aqueous complexes with dissolved organic matter (DOM). The dis-
solved organic carbon in the sludge supematant was 5162 #tool L - l (~62 mg
L - 1) (Table II). The content of DOM in the supematant was estimated by assum-
ing a carbon content of 31% in the organic matter of the supematant (Sommers,
1977). The number of binding sites on the DOM was estimated to be 6x 10 - 4
moles per gram organic matter (Susetyo et al., 1990). Based on these assumptions,
the binding capacity of the DOM for the metals was estimated. Some error may
exist in this estinaation because of different chemical characteristics of the DOM
in soil compared to sewage supernatant. The actual metal complexation may also
differ from those estimated by aqueous speciation calculations because MINTE-
QA2 makes assumptions about strength of the metal-DOM complex. However, the
purpose of the computation was to compare the results of the sorption study and
predict the stability of metal complexes with soil organic matter. The percentage
of DOM-metal complexes estimated by MINTEQA2 were: Pb, 54%; Cu, 54%;
Zn, 6%; Ni, 4% and Cd, 3% at pH 4.5 and Cu, 69%; Pb, 63%, Zn 15%; Ni, 10%
and Cd, 7% at pH 6.5 which qualitatively agrees with the distribution coefficient
342 SUI)UAN GAO l'2TAL.

Table VI
Percentage ot aqueous metal specms ill
sludge effluent, computed by MINTEQA2
at total metal concentration of 5(} itmoI L I

pH 4.5 pH 6.5

CrOf 2 1.3 55.7

HCrO]- 97.7 41.6
NaCrOa <1.0 2.4

Ni +-~ 89.9 76.3

Ni-DOM 3.9 10.3
NiAc 6.0 13. I

Cu +2 31.5 12.8
Cu-DOM 54.4 68.8
CuAc 13.0 13.5
Cu{OH )2 < I.(} 1.8
CuAc2 1.0 2.7

Zn +2 85.9 68.5
Zn-DOM 5.9 14.7
ZnAc 7.9 16.2

Cd +2 73.1 54.0
Cd-DOM 3.2 7.3
CdCI + 7.5 5.5
CdAc 15.4 29.3
CdAc~ < 1.0 3.8

Pb 2+ 15.6 5.8
Pb-DOM 53.6 62.6
PbAc 28.6 27.5
PbAc2 1.4 3.5

(Kd) trend (Pb~Cu>Zn>Ni~Cd) of our study (Table VI). These results support
the hypothesis that formation of organo-lnetal complexes may be the dominant
adsorption and solution complexation mechanism for these metal cations.
The dissolved organic matter in the supernatant will also be subjected to adsorp-
tion and partitioning in the solid phase. Dissolved organic matter can be adsorbed
rapidly on the soil and attains a steady state in a few hours (Dahlgren and Marrett,
1991 }. The DOC concentrations in the solution phase during metal adsorption was
not monitored in this study. Because the organic solid-phase appears to have a
higher affinity for metals than the mineral phase, the inetal adsoFption is related to
soil organic matter at low metal concentrations. It is expected that once the organic
 SIMULTANEOUS SORPTION OF Cd, Cu, Ni, Zn, Pb, AND Cr ON SOILS 343

phase is saturated, metal sorption may be more closely related to other phases.
Thus, the correlation of metal sorption to soil organic mater may hold only for
certain conditions.
The adsorption of Pb, Cu, Zn, Cd and Ni was higher at pH 6.5 than at pH 4.5,
which is in agreement with previous studies (Santillan-Medrano and Jurinak, 1975;
Sadiq, 1981; Kurdi and Doner, 1983). Free ion concentrations of these metals are
predicted by MINTEQA2 to decrease and the amount of metal complexes with
DOM increase as pH increases from 4.5 to 6.5 (Table VI). Metal complexes with
z~cetate also increase from pH 4.5 to 6.5 while hydroxyl forms of the metals are
negligible. At high pH, the stronger adsorption results from the dissociation of
l'unctional groups on the organic phase due to less competition from H +. Thus,
the sorption trend of the metals was a result of a combination of metal complexes
with both DOM in the solution phase and organic matter on the solid-phase, as
well as competition among metal ions. In the case of disposal of sewage sludge,
high organic matter concentrations are introduced to the soil system. The dissolved
organic matter could be adsorbed rapidly on the soil.
Chromium was the most weakly adsorbed ion among all the elements investi-
gated and there was no correlation between chromium sorption and soil organic
matter content at either pH 4.5 or 6.5. This is due to the hexavalent form (CrO]-
or HCrO4 -) added to the supernatant in this study. The CrO~- fraction increases
and HCrO 4 decreases as pH changes from 4.5 to 6.5 (Table VI). Its adsorption
should decrease as pH increases due to the increase of negative charge on the solid
phase. In contrast to theory, sorption of chromium was higher at pH 6.5 than at
pH 4.5; however, the variation was not as large as for other metals. It is possible that
reduction of chromate to Cr 3+ occurred during the experiment, and this species is
much less soluble. The reduction of Cr(VI) is enhanced at lower pH values (James
and Bartlett, 1983a, b; Eary and Rai, 1991).
Lead was the most strongly adsorbed element in this study. Less than 2% of the
total Pb was in the solution phase at equilibrium when 50 #mol L-I was added to
the soil solution (Table V). Studies of lead chemical fractionation and solubility on
three surface soils containing high Pb levels showed that less than 0.7% of the Pb
was in an exchangeble form (Garcia-Miragaya, 1984). Therefore, lead was present
dominantly in nonexchangeble forms associated primarily with the organic and
residual [u in two of the three soils and predominantly specifically bound to
inorganic sites in the third soil. Computation results using MINTEQA2 (Allison et
al., 1991 ) in our study predicted that 99% of the Pb partitioned in the solid phase.
Cadmium and nickel are weakly adsorbed metals. Cadmium contamination
has the greatest potential for limiting application of sludge on land because of
its relatively high mobility in the soil environment (Page and Chang, 1981). The
sorption of Cd was studied by Cline and O'Connor (1984) in three soils that were
unamended, freshly amended, or pre-conditioned with gamma-irradiated sewage
sludge. Result showed that Cd sorption was greatest in the unamended soils, less
344 SUDUAN GAOETAL.

in soils preconditioned with sludge, and the least in the freshely amended soils. No
adequate explanation could be given to the treatment effects.
The distribution coefficients for metals in this study involved competition effects
since all the metals were added simultaneously to the soil system. Comparison
among Kct values (Table III) for all soils and the amount of metal adsorbed at
the 50 ILmol L - l addition (Table V) indicates the following selectivity of metals:
P b > C u > Z n > N i > C d ~ C r at pH 4.5 and P b > C u ~ Z n > C d > N i > C r at pH 6.5. Lead,
Cu, and Zn are most strongly adsorbed and Cd, Ni, and CrO4 are weakly adsorbed.
Therefore, leaching of Cd, Ni, and CrO4 is most probable for the soils studied.
In addition, increasing ionic strengths decrease metal sorption because of the
competition by other cations for adsorption sites (Petruzzelli et al., 1985). Thus,
soils with higher ionic strength may have more risk of metal leaching from sewage
sludge disposal than soils with lower ionic strength.
Disposal of sewage sludge in this study is unlikely to increase leaching of
Pb, Cu, Zn in these soils in the short term, especially due to the near neutral to
alkaline pH values. The risk of elevating certain element levels such as Cr, Cd and
Ni still exists depending on the sorption capacity of the soil, the composition of
sewage sludge, and application rates and frequency. The metal sorption strength
at low metal loadings was related to organic matter concentrations and surface
area. This suggests that soil organic matter plays an important role as well as pH.
Further, disposal of sewage sludge has been reported to raise soil organic matter
concentrations, which may alleviate the risk of metal contamination to a certain
extent. However, long term effects of sewage sludge disposal on the environment
need further studies under specific environmental conditions.

References

Allison, J. D., Brown, D. S. and Novo-Gradac, K. J.: 1991, MINTEQA2IPRODEFA2, A Geochemical

Assessment Model for Environmental Systems: Version 3.11. U.S. EPA. Athens, Georgia.
Behel, D. Jr, Darrell, D. W., Nelson, E. and Sommers, L. E.: 1983, J. Era,iron. Qual. 12, 181.
Boyd, S. A., Sommers, L. E. and Nelson, D. W.: 1981, Soil Sci. Soc. Am. J. 45, 1241.
Carter. D. L., Mortland, M. M. and Kemper, W. D.: 1982, 'Specific surfaces', in A. Klute (ed.) Methods
~?["Soil Analysis. Part l-Physical and Mineralogical Metho~L~', 2nd ed. Soil Science Society of
America, Madison, Wisconsin, pp. 413-423.
Chairidchai, R and Ritchie, G. S. E: 1990, Soil Sci. Soc. Am. J. 54, 1242.
Chang, A. C., Page, A. L., Warneke, J. E., Resketo, M. R. and Jones, T. E.: 1983, J. Em'bwn. Qual.
12, 391.
Cline, G. R. and O'Connor, G. A.: 1984, Soil Sci. 138, 248.
Dahlgren, R. A. and Marrett, D. J.: 1991, Soil Sci. Soc. Am. J. 55, 1382.
Eary, L. E. and Rai, D.: 1991, SoilSci. Soc. Am. J. 55, 676.
Elrashidi, M. A. and O'Connor, G. A.: 1982, Soil Sci. Soc. Am. J. 46, 1153.
Elliott, H. A. and Denneny, C. M.: 1982, J. Era,iron. Qual. 11,658.
Garcia-Miragaya, J.: 1984, Soil Sci. 138, 147.
Gee, G. W. and Bauder, J. W.: 1986, "Particle-Size Analysis', in A. Klute (ed.), Methods of Soil
Analysis. Part 1-Physical and Mineralogical Methods, 2nd ed. Soil Science Society of America,
Madison, Wisconsin, pp. 383-411.
Harter, R. D.: 1992, Soil Sci. Soc. Am. J. 56, "444.
 SIMULTANEOUSSORPTION OF Cd, Cu, Ni, Zn, Pb, AND Cr ON SOILS 345

i~olmgren, G. G. S.: 1967, Soil Sci. Soc. Am. Prvc. 31,210.

Inskeep, W. P. and Baham, J.: 1983, Soil Sci. Soc. Am. J. 47, 1109.
James, B. R. and Bartlett, R. J.: 1983a, J. Environ. Qual. 12, 173.
James, B. R. and Bartlett, R. J.: 1983b, J. Environ. Qual. 12, 177.
Kuo, S. and Baker, A. S.: 1980, Soil Sci. Soc. Am. J. 44, 969.
Kurdi, F. and Doner, H. E.: 1983, Soil Sci. Soc. Am. J. 47, 873.
McKeague, J. A. (ed.): 1976, Manual on Sampling and Methods ~/'Analysis, Soil Res. Inst., Agricul-
ture Canada, Ottawa.
Nelson, R. E.: 1982, 'Carbonate and Gypsum', in A. L. Page (ed.), Methods of Soil Analysis. Part
2-Chemical and Miclvbiological Properties, 2rid ed. Soil Science Society of America, Madison,
Wisconsin, pp. 181-197.
Page, A. L. and Chang, A. C.: 1981, 'Trace Metals in Soils and Plants Receiving Municipal Wastewater
Irrigation', in F. M. D' Itri (ed.), Municipal Wastewater in Agriculture, Academic Press; New York,
pp. 351-372.
Petruzzelli, G., Guidi, G. and Lubrano, L.: 1985, Commun. Soil Sci. Plant Anal. 16, 971.
Sadiq, M.: 1981, Commun. Soil Sci. Plant Anal. 12, 619.
Santillan-Medrano, J. and Jurinak, J. J.: 1975, Soil Sci. Soc. Am. Prw'. 39, 851.
Soil Survey Staff: 1984, Procedures for Collecting Soil Samples and Methods of Analysis for Soil
Survey. Soil Survey Investigations, Rep. No. 1. USDA-SCS Agric. Handb. 436. U.S. Government
Printing Office, Washington DC.
$ommers, L. E.: 1977, J. Environ. Qual. 6, 225.
Sposito, G., Lund, L. J. and Chang, A. C.: 1982, SoiISci. Soc. Am. J. 46, 260.
Sposito, G., Holtzclaw, K. M. and LeVesque-Madore, C. S.: 1979, Soil Sci. Soc. Am. J. 43, 1148.
Sposito, G., Holtzclaw, K. M. and LeVesque-Madore, C. S.: 1981, Soil Sci. Soc. Am. J. 45, 465.
Sposito, G. and Mattigod, S. V.: 1979, GEOCHEM: A Computer Program for the Calculation of
Chemical Equilibria in Soil Solutions and Other Natural Water Systems. Dep. Soil and Environ.
Sci., University of California, Riverside.
Susetyo, W., Dobbs, J. C., CarTeira, L. A., Azarraga, L. V. and Grimm, D. M.: 1990, Anal. Chem. 62,
1215.
Whittig, L. D. and Aliardice, W. R.: 1986, 'X-Ray Diffraction Techniques', in A. Klute (ed.), Methods
of Soil Analysis. Part 1-Physical and Mineralogical Methods, 2rid ed. Soil Science Society of
America, Madison, Wisconsin, pp. 331-362.