Interfacial Reactions and the Fate of Heavy Metals in Soil-Water Systems

Author(s): C. P. Huang, H. A. Elliott, R. M. Ashmead

Source: Journal (Water Pollution Control Federation), Vol. 49, No. 5 (May, 1977), pp. 745-756
Published by: Water Environment Federation
Stable URL: http://www.jstor.org/stable/25039346
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Interfacial reactions
and the fate of heavy metals
in soil-water systems
C. P. Huang, H. A. Elliott, R. M. Ashmead
University of Delaware, Newark

Public concern over heavy metal pollution tion of metal-containing wastewater to land
has grown since the outbreak of as treatment and disposal is, however, very
constantly
Minamata disease caused by the mercury in little explored. The major objective of this
Japan.1?2 Man's awareness of the
heavy metal work is to investigate the fate of heavy metals
hazard now covers a wide spectrum of metals in the soil-water system. Four heavy metals,
such as lead, cadmium, chromium, silver, cop including copper, zinc, lead, and cadmium,
4 were
per, and zinc.3, Trace amounts of these heavy studied. The heavy metal adsorption
metals can be beneficial to microorganisms5 characteristic of and two Dela
y-Al203, Si02,
and plants,6-8 but the presence of heavy metals ware soils (Metapeak and Evesboro) were
at relatively high concentrations in the en investigated in the laboratory. The effect of
vironment has been to be detri pH and anions on the adsorption reaction was
already proven
mental to all living systems. This concern is examined.

augmented by the fact that most metals are

widely dispersed and can persist in the en INTERFACEAND INTERFACIAL
vironment for a long time. REACTIONS
To curtail heavy metal pollution problems, Solid-solution interface. In order to ap
engineers and scientists have developed pro preciate the fate of heavy metals in the soil
cesses and measures for the treatment and water system, it is important to understand

disposal of metal-containing wastes, namely, the general characteristics of soil and the
chemical ce of metals in an aqueous
precipitation, electro-deposition, chemistry heavy
mentation, solvent extraction, ultrafiltration, solution.
activated carbon 4? 9 The soil is the product of climate and liv
ion-exchange, adsorption,3?
and biological processes.10?X1 However, none ing organisms acting on rocks, and its nature
of these processes is yet economically feasible, is determined by the parent rocks and the
and none will ultimately dispose of the metal forces acting on them. Regardless of its het
laden wastewaters on a large-scale basis. erogeneity, the constituents of soil can be
Because of its dynamic and heterogeneous subdivided into coarse fraction (>2 jjm),
nature, soil can react with a broad spectrum colloid fraction (<2 /?m), and organic frac
of extraneous components. The nature of tion.7 The coarse fraction constitutes 5 to
these reactions is such that soil may function 90 percent (dry weight) of soils and may be
as a medium for either waste storage or for into gravel, sand, and silt by siev
separated
ultimate waste disposal.12?13 However, at the ing. This fraction is primarily responsible for
current stage of development, two general tech the filtration mechanism of soils. The col
nical problems still remain to be solved: the loidal fraction constitutes 10 to 80 percent
effects of heavy metals on crops and their po (dry weight) of most soils and is responsible
tential danger to groundwater quality. In the for the color, texture, and ion-exchange prop
strict sense, ultimate disposal of waste products erties of many soils. It is well known that
should accomplish a permanent removal with aluminum, silicon, and iron are the major ele

possibility of recycling and reuse. ments of soils.

Recent progress made on land application In addition to these inorganics, soil con
of domestic waste to forest and crops has tains 1 to 40 percent (dry weight) organic
cast some promising light on soil treatment matter. This fraction covers a large number
of metal-laden wastewater.12?13 The applica of small organic molecules, many of which

May 1977 745

Huang et al.

dissolve in the soil water, and insoluble poly 90 percent of the heavy metal in anaerobically
meric organic matter, humus. In many soils, digested sludge was found in the particulate
90 to 99 percent of the total carbon, nitrogen, fraction (>100 /?m) and that a high correla
and sulfur is bound in the humus fraction. tion exists between heavy metal content and
Humus particles are of colloidal characters volatile solids, but no such relationship was
and bind strongly to clays and hydrous oxides. observed for inert solids.19 Chen et al re
Humus also has cation-exchange proper ported that the suspended particles from ur
15 were
ties.14? Soil organic matters can react with banized drainage channels found to con
or chelate a number of metal elements.16?17 tain heavy metals in the same magnitude as
The small organic molecules present in soil the suspended particles from wastewater
include a great variety of compounds but are effluents.20

predominantly acidic. They are the products In a soil-water system, the fate of heavy
of partial decomposition of organic matter by metals is directly related to their states of
bacteria and fungi and include the common identity and the existing environmental con
amino acids, acetic, butyric, citric, formic, 2 ditions. Figure 1 shows the schematic model
keto-glucomic, malic, oxalic, tartaric, and a of heavy metal transformation in a soil-water
variety of lichen acids. The major effects of system. The free and complexed metal ions
these acids are the lowering of the soil solu may be removed from solution by adsorption
tion pH, and the increase in the rate of the and precipitation mechanisms, while the par
mineral dissolution and the extent of chelation ticulate heavy metals may be transformed by
which, in turn, renders the soil minerals more their own dissolution and filtration mechanism
soluble.15 of soils.
Interfacial reactions. In the aquatic en Dissolution versus precipitation. In principle,
vironment, heavy metals may be classified into the concentration of heavy metals in aqueous
at least two different categories: (a) in true system is controlled by the congruent and
solution as free or complexed ions and (b) incongruent solubility of various oxides, car
in particulates from adsorption onto other par bonates, sulfates, and sulfides. Table I lists
ticles, or incorporation into the biomass of some of the solids and aqueous species com

living organisms and inorganic precipitates monly found in aqueous system.21?22

such as hydroxides, sulfides, and The aqueous include
carbonates, species mostly hydroly
sulfates. Many metals in the wastewater are sis products and organometallic compounds.
found in very insoluble sulfide (Zn, Ag, Hg, The equilibrium constants of all species are
Cu, Cd, Pb) and oxide (Cr, Fe) forms, while also shown in Table I. It is also important
some (Ni, Co, Mn) are relatively soluble.18 to note that complex formation and chela
Gould and Genetelli reported that more than tion can render solid metal compounds more

\X-B , mi X-AY
rx ; L"Y ; OH" ; e~ ; M?O!!)*-0 ; ML*

WATER
mi X-AY
aL"y CPX. "LA L-Y ?l?:??1)y(s)
(A+l)
u+x eOR" ruor,)x" OH" OH)*
n(OH)x-(B+1)(s)
CPX.

RQX.
b" H (s)
ce"

ISOLIDSl

FIGURE 1. Schematic model of metal ions transformation in soil-water system.

CPX = complex formation, PCX = precipitation, DIS = dissolution, ROX = reduction
oxidation ADX = DES =
reaction, adsorption, desorption.

746 Journal WPCF

 Heavy Metals

TABLE I. Chemical equilibria and equilibrium constants of heavy metal-related

species21-22
?
Equilibria log K

Copper :

Cu2+ + H20 = Cu(OH)+ + H+ 10

H+ = 2Ca2+ + H20 -6.82
Cu(OH)33+ +
20H- = 26.71
Cu(OH)22+ + 2Cu2(OH)2
Cu2(OH)2C03(s) + 4H+ = 2Cu2++ 3H20 + C02(g) 14.16

Cu3(OH)3(C03)2(s) + 6H+ = 3Cu2++ 4H20 + 2C02(g) 21.24

Cu2+ + = 6.77
CO32- CuC03(aq)
Cu2+ + = 10.01
2C032~ Cu(C03)22-(aq)
= Cu2+ + H20 7.65
CuO(s) + 2H+
Cu2+ + 2e = Cu(s) 12.0
Cu2(OH)2C03(s) + 4H+ = 2Cu2++ 2H20 + H2C03 12.64
= 4Cu2+ + S042" + 6H20 15.20
Cu4(OH)6S04(s) + 6H+
= 3Cu2++ S042" -f 4H20 8.80
Cu3(OH)4S04(s) + 4H+
CuS(s) + 2H+ = Cn2+ + H20 15.17
Cu2S(s) + 2H+ = 2Cu2++ H2S + 2e 33.08

Zinc:
Zn2+ + 30H- = 13.9
Zn(OH)r
Zn2+ + 40H- = 15.1
Zn(OH)42~
Zn2+ + OH" = 5.04
Zn(OH)+
Zn2+ + 20H- = 6.0
Zn(OH)2(aq)
= Zn2+ 2e 25.79
Zn(s) +
ZnO(s) + 2H+ = Zn2+ -f H20 10.99
ZnS(s) + 2H+ = Zn2+ + H2S -4.16
= Zn2+ -9.82
ZnC03(s) + C032~
= 4Zn2+ + 60H~ -53.6
Zn4(S04)(OH)6(s) SO,2" +

Cadmium :
Cd2+ + 20H- = Cd(OH)2(s) 14.0
Cd2+ + H20 = Cd(OH)+ + H+ -7.92
=
Cd(OH)+ + H20 Cd(OH)2(aq) + H+ -11.30
=
Cd(OH)2(aq) + H20 Cd(OH)r + H+ -14.3
Cd(s) = Cd2+ + 2e 12.16
CdO(s) + 2H+ = Cd2+ + H20 15.73
=
CdS(s) + 2H+ Cd2+ + H2S(aq) -5.73
= Cd2+ + H2C03 5.40
CdC03(s) + 2H+
= 4Cd2+ + 60H~ S042~ -50.0
Cd4(OH)6S04(s) +

Lead:
= Pb2+ -15.3
PbO(s) + H20 -f 20H-
PbO(s) + H20 + OH- = Pb(OH)r -1.4
=
PbO(s) + H20 Pb(OH)+ + OH- -7.46
= -4.4
PbO(s) + H20 Pb(OH)2(aq)
Pb2+ + 40H- = 16.3
Pb(OH)42"
Pb02(s) + 4H+ + 2e = 2H20 + Pb2+ 49.2
= Pb2+ + H20 12.7
PbO(s) + 2H+
Pb(s) = Pb2+ + 2e 4.26
= Pb2+ + S2" -28.08
PbS(s)
= Pb2+ -7.87
PbS04(s) + S042-
= 3Pb2++ 2C032+ + 20H- -18.8
Pb3(C03)2(OH)2(s)
= Pb2+ -12.83
PbC03(s) -f- CO,2"

Glycine, H2L:
= H+
H2L + HL" -2.34
HL- = H+
+ L2" -9.60
Cd2+ + U- = CdL 4.27

May 1977 747

 Huang et al.

TABLE I. (Continued)
Equilibria ?log K

Glycine, H2L:

Cd2+ + 2L2" = CdL22~ 4.46

Cd2+ + L2" = CdL 8.12
Cd2+ + 2L2" = CdL22~ 6.91
Pb2+ -f L2" = PbL 5.47
Pb2+ + 2L2" = PbL22~ 3.39
Zn2+ + L2- = ZnL 5.16
Zn2+ + 2L2- = ZnL22~ 4.34

Tartaric acid, H2L:

= H+
H2L + HL" -2.88
HL- = H+
+ L2" -3.94
Cd2+ + 2L2" = CdL22~ 4.49
= CuL
Cu2+ + L2" 3.2
Cu2+ + 2L2" = CuL22~ 1.91
= PbL
Pb2+ + L2- 3.78
= ZnL 2.68
Zn2+ + L2-
Zn2+ =
+ 2L2- ZnL22" 5.64

Nitrilotriacetate, H3L:
= H+ -1.89
H3L + H2L-
= H+ HL2~ -2.49
H2L- +
HL2~ = H+ + L3- -9.73
Cd2+ + U- = CdL1" 9.54
Cu2+ + L3" = CuL1" 12.68
Pb2+ + L3- = PbL1- 11.8
Zn2+ + L3- ? ZnL1" 10.67

Phosphate, H3L:
= H+ -2.17
H3L + H2L-
= H+
rJ2L + HL2" -7.21
HL2" = H+ + L3" -12.36
3Cd2+ + 2L3" = Cd3L2(s) -32.6
3Cu2+ + 2L3" = Cu3L2(s) -36.9
3Pb2+ + 2L3" = Pb3L2(s) -9.90
3Zn2+ + 2L3" = Zn3L2(s) -32.04

Sulfur :
= H+
H2S + HS- -7.00
HS- = -14.00
H+-fS2"
- 8H+ + 6e -36.2
S(s) + 4H20 S042~ +
S(s) + 2H+ + 2e = H2S 4.8

Carbonate :
= H+ -6.30
H2C03 + HCO3-
= H+ -10.30
HCOr + C032~

soluble. The effect of organic ligands on the energy sources. Sequential oxidation of or

solubility of heavy metals has been extensively ganic compounds mediated by microbial activ
investigated.22?23 ities will change the environment from an
Dissolution of relatively insoluble substances aerobic to an anaerobic one. Consequently,
from soil through biological activities may also inorganics are reduced at various stages of
contribute to the chemical composition of soil organic oxidation to yield electron-acceptors.
water. Microorganisms have been known to For instance, the reduction ?f manganese di
use organics and inorganics as carbon and oxide to manganese carbonate is followed sue

748 Journal WPCF

 Heavy Metals

ri

Zfi4?>H)((S%\)
7 | ZnO llTJ ?S \Ze

; cas c?
a/owVH) \ceOtaco, J

2?\

f?
|b?TT
I *?q jUrrHj ptoo, M
i
pbo2 jp*vto^^: j pbco, pbs^ j Pb n>
CCu?] fH-5

FIGURE 2. Solubility of solid heavy metal compounds as function of pc. (a) Zinc
and cadmium systems; (b) copper and lead systems. Concentrations of total carbonate
and sulfur are 10-3 M individually.

cessively by the reduction of nitrate, ferric and Cd4(OH)6(S04), in aerobic conditions

hydroxide, alcohol, carbohydrate, sulfate, sul and of PbS, CuS, CdS, and ZnS in anaerobic
fur, and carbon dioxide. The reduction in the conditions, respectively. Since the effect of
redox potential in the soil-water system may organic chelation is not accounted for, this
solubilize heavy metals. Figure 2 demon prediction can only be an approximation.
strates the solubility (at pH 5) of heavy metal More details of the computation procedure for
solids (carbonate, sulfates, oxides, and Sul pc-stability can be found elsewhere.23
diagram
fides) as a function of the redox potential Adsorption. The abundance of oxides, hy
(pe). The data show that at pH 5 and total droxides, and clay minerals in most soils is the
carbonate and total sulfur concentrations of primary determinant of their ion exchange
10~3 mol/1 each, the concentration of free lead, mechanism. The exchange reaction, in fact,

copper, zinc, and cadmium is controlled by the differs from adsorption; however, because
solubilities of PbS04, CuO, Zn4(OH)6(S04), nearly every ion-exchange process is accom

May 1977 749

 Huang et al.

panied by adsorption and desorption, adsorp 6 to 7 (cadmium) and 5 to 6 (lead, zinc, cop
tion sometimes is indistinguishable from ion per). The abrupt increase in adsorption den

exchange. sity correlates with the presence of M2+. As

Various theories have been advanced to pH continues to
increase, chemical precipita
describe and interpret metal ion interaction tion becomes a dominant mechanism in heavy
at solid-solution interface.24 and metal removal. When decreases to be
MacNaughton pH
James proposed that heavy metals are removed low this range, of copper and zinc
adsorption
from aqueous solution by three mechanisms.25 becomes inappreciable, while lead and cad
These include the ion exchange reactions: mium become negatively adsorbed. The or
der of adsorption increases in the following se
m(=S- OH) + M+* quence, Cu(II) > Zn(II) > Pb(II) > Cd(II)
-
<-> (=S 0)m M*-m + mH+ (1) for all solids.
the adsorption and hydrolysis at the surface This finding agrees well with the work of
Lindsay and Norvell, who reported for the ad
= S - OH + mH20 + M+* of zinc on soil a stoichiometric rela
sorption
-
<=?== S M (OH)m+i*-m + mH+ (2) tion,26

and hydrolysis followed by an adsorption re Zn2+ + soil <=?Zn - soil + 2H+

action:
and the work of others.23?27 Hohl and
M+* + Stumm 24 reported that the interaction between
mHaO^MtOH)^-?1 + mH+;
Pb(II) and y-Al203 involves specific binding
M(OH)m*~m + s S- OH of Pb2+ ions on the hydrous y-Al203
surface.
<=>=S- M(OH)m+1*"m (3) They interpreted this interaction as surface
complex formation.
where :
= A10H + Pb2+ = AlO Pb+ + H+ (4)
sS- OH
=
hydrated soil surface, 2(=A10H) + Pb+ = (=A10)2Pb+ 2H+ (5)
Hydrolysis need not be invoked to describe
(=S-0)mM*-m
= metal ion adsorbed at
the interaction. MacNaughton and James,25
hydrated soil
however, reported that Hg(OH)2(aq) was the
surface,
major speceis being adsorbed by Si02.
sS- No observation of negative adsorption by
M(OH)m+1-m
= metal at
soils and oxides has ever been reported.
hydroxyl species adsorbed
Huang has reported negative adsorption in
hydrated soil surface, 29
silicic and tryptophan-CaC03
acid-y-Al203,28
M(OH)mm-*
interactions. Van de Hull has also used the
=
hydroxyl metal species, and negative adsorption principle to evaluate the
surface area of suspended Most in
particles.
M+* ert electrolytes were reported to be negatively
= free metal adsorbed by most soil minerals.30
ion.
The effect of solids on heavy metal adsorp
These three models are, in fact, indistin tion is shown in Figure 4. Again, it clearly
guishable unless measurements are undertaken shows that at low pH range, cadmium and
to cover more than the solution metal ion con lead are negatively adsorbed by all solids,
centration, pH, or the and
adsorption capacity while copper and zinc exhibit positive ad
the type of bonding at the surface. This work
sorption characteristics. This effect of solids
aims at the investigation of heavy metal ad can be, in part, described by the difference
at solid-solution interface.
sorption in zero point of charge,
pHzpc (Figure 5).
The pHzpc was found to be 8.5 ?0.23, 2?
ADSORPTIONOF HEAVYMETALS ON 0.2, 2.3 ? 0.2, 2 ? 0.2 for 7 A1203, Metapeak,
HYDROUSOXIDES AND SOILS Evesboro, and Si02, respectively. It demon
Effects of pH and solids types. The adsorp strates that solid characteristics alone cannot
tion of 10-3 M heavy metals (Cu, Zn, Pb, Cd) dictate the whole The
adsorption picture.
from aqueous solution of 0.1 M ionic strength electrostatic model of adsorption predicts that
(NaCl) onto hydrous oxides and soils is shown for a given
heavy metal, the order of adsorp
in Figures 3 and 4. It can be seen that ad tion density should increase in the order Si02
sorption increases abruptly in the pH ranges > Evesboro > Metapeak ? A1203. No such

750 Journal WPCF

 Heavy Metals

FIGURE 3. Adsorption of heavy metals on oxides and soil minerals, (a) Si02;
(b) y-Al203; (c) Metapeak; (d) Evesboro. Concentrations of solid, heavy metals
and ionic strength are 5g/l, 10~3 M (from chloride salt except zinc, which was pre
pared from sulfate salt) and 101 M (from NaCl), respectively. Adsorption was
measured after 24 h of on a machine, metals were ana
mixing gyrotation heavy
lyzed by atomic absorption spectrophotometer.

May 1977 751

 Huang et al.

E
a?

H-h
3 4 5 6 7 9 9

2oo,

3
?-1-i-1-1-1-1 6 7S?

FIGURE 4. Adsorption of heavy metals on various solids, (a) Copper; (b) zinc;
(c ) lead; (d ) cadmium. Data were plotted from Figure 3.

752 Journal WPCF

 Heavy Metals

o
^?L203
SiOg
METAPEAK
EVESBORO

i+

! I. *

1+

3+

FIGURE 5. Electrokinetic characters of solids. The electrophoretic mobility was

measured in 10"1M NaCl ionic strength by zeta meter.

order was observed, for the adsorption soil-water contains many organic substances
except
of zinc. In general, y-Al203 shows the least that may influence greatly the adsorption of
adsorption capacity for all metals except the heavy metals. Figures 7 and 8 show the ad
cadmium ions. It is important to realize that sorption of heavy metals as influenced by some
many factor besides the pHzpc can modify the anions such as phosphate, glycine, tartaric acid,
adsorption of heavy metals. An important nitrilotriacetate and humic acid.

parameter that must be accounted for is the In the presence of anions, adsorption of

equilibrium chemistry of heavy metals in aque heavy metals is more pronounced. Anions
ous solution. For instance, lead and cadmium enhance heavy metal adsorption at low pH
oxides are more soluble than those of copper values, at which adsorption is not likely to
and zinc at the pH range of adsorption, or the occur in their absence. A sequence of ef

hydrolysis products of copper and zinc ap fectiveness for the compounds investigated is
pear at a lower pH value (Figure 6). The humic acid > nitrilotriacetate > glycine? tar
results do reveal that copper and zinc are more trate > Under most circumstances,
phosphate.
adsorbable than lead and chromium. ions are less effective than the or
phosphate
This finding is rather striking. From the The role of anions in the
ganic compounds.
agronomical point of view, zinc and copper of heavy metal ions can be de
adsorption
can be rendered unavailable for plant uptake.
lineated by considering the following separate
Lead and cadmium may accumulate in the
reaction steps 31:
water rather than at the interface. It is very
1. Anions accumulate in the double layer
likely that, at low pH, groundwater may be
contaminated by lead and cadmium, and crops of a positively charged particle. This step is
are from and zinc rather fast, and is accompanied by a compen
suffering copper deficiency.
Effect of anions. As discussed above, the sation of the double layer potential.

May 1977 753

Huang et al.

-44

FIGURE 6. Stability diagram of heavy metal oxides. Curves were computed from
equilibrium constants.

2. The approach of metal ions to the soil Another interpretation is that there is for
surface is facilitated. mation of metal-ligand associates at first, fol
3. Complexes, or very likely chelates, form lowed by the adsorption of these organometal
between heavy metal ions and the already lic compounds by the hydrous solid through
absorbed aqueous anionic ligands. specific chemical bonds such as sharing of free

J_ M?TAPEAK-Cd

BLANK
O PHOSPHAT!
A GLYCINE
A TARTRATE
IACETATE
N IT?ILOT*
D HUMIC ACIO

FIGURE 7. Effect of anions on the adsorption of heavy metals by Metapeak. (a.)

Cadmium; (b) copper. In addition to the experimental conditions shown in the
caption of Figure 3, the anion concentration was 10-4 M and the humic acid was added
at 50 mg/1 level.

754 Journal WPCF

 Heavy Metals

sides the tendency of complex formation, the

steric effect of metal-ligand associates must
also an essential role in promoting metal
play
adsorption.

SUMMARY
It is possible to identify the following pro
cesses and factors that govern the fate of heavy
metals in the soil-water system.
1. Dissolution-precipitation: The congruent
and incongruent solubility of the oxides, hy
droxides, sulfates, sulfides, and carbonates of

heavy metals can contribute to the chemical

constituents of soil-water. This process is in
fluenced by pH, pe, the amount of carbonate
and sulfur present, and to a great extent the

presence of organic substances. The forma

tion of metal-chelates or metal-complexes can
render metal solids more soluble. Microorga
nisms, whose metabolic activities tend to mod

ify the redox potential of the soil-water sys

tem and contribute organic acids, can influence

significantly the solubility of metal solids.

2. Adsorption: Interfacial association be
tween heavy metals and soil minerals is con
sidered the most important process in regu
lating the concentration of heavy metals in the
soil-water environment. Copper and zinc are
FIGURE 8. Effect of humic acid on the ad more removable than lead and cadmium.

sorption of lead by Metapeak. Experimental When the solid surfaces are very positively
conditions were the same as for Figure 7. charged, positive lead and cadmium ions are

expelled away from the interface and result

com
in an excess of metal ions in the bulk phase
electrons available from the metal-ligand
of the soil-water system.
plexes and hydrogen bond. This second model
is more likely because, kinetically, metal-ligand
association should take place at a faster rate REFERENCES
1. Kiyoura, R., "Water Pollution and Minamata
than solid-ligand combination. However, with
Disease." In "Advances in Water Pollution
the presently available measure
laboratory Proc. 1st Intl. Water
Research." Conf.
ments, it is still impossible to reveal the mecha Poll. Res., Pergamon Press, London, Eng
nism of metal adsorption enhancement by land, Vol. 3, p. 291 (1964).
anions.
2. Jrakayama, K., "The Pollution of Minamata
The difference in effectiveness on heavy
Bay and Minamata Disease." In "Advances
metal adsorption of anions studied reflects, in in Water Pollution Research." Proc. 3rd
part, the tendency for complex formation be Intl. Water Poll.
Conf. Res., Pergamon
tween metal ions of question and the anionic Vol.
Press, London, England, 3, p. 153,
ligands. Table I also shows the stability con (1966).
stants of the possible organometallic com
3. Dean, J. G., et al., "Removing Heavy Metals
plexes. It is seen that phosphate, which gives from Wastewater." Environ. Sei. ir
no evidence of forming with the .518
complexes Technol, 6, (1972).
four metals studied, has the minimum effec 4. Argaman, Y., and Weddle, C. L., "Fate of
tiveness. Metals in Physical-Chemical Treat
Heavy
A study of cation adsorption onto hydrous ment Processes." Amer. Inst. Chem. Eng.
32 found that 400
y-Al203 by Huang organic phos Symp Ser., Water, 70, 136, (1973).
phate (atp) is more effective than inorganic 5. Wood, D. and Tchobanoglous, "Trace
K., E.,
phosphate; glycine is more operative than di Elements in Biological Waste Treatment."
glycine, which is even more influential than Jour. Water Poll. Control Fed., 47, 1933

trigylcine. It becomes apparent that, be (1975).

May 1977 755

Huang et al.

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756 Journal WPCF