(IOlh-7017 80 I lO-l7olso?

i)o 0

Sorption of metals on humic acid*

H. KERNDORFF~ and M. SCHNITZER$
Chemistry and Biology Research Institute, Agriculture Canada, Ottawa,
Ontario, Canada KIA OC6

Abstract--The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II).
Fe(III). Ph. Cu, Al. Ni, Cr(III), Cd, Zn. Co and Mn, was investigated with special emphasis on effects of
pH. metal concentration and HA concentration. The sorption efficiency tended to increase with rise in
pH. decrease in metal concentration and increase in HA concentration of the equilibrating solution At
pH 2.4. the order of sorption was:

Hg > Fe > Pb > Cu=AI z Ni > Cr=Zn=Cd=Co=Mn

At pH 3.7. the order iv;,?:

Hg=Fc>AI>Pb>Cu>Cr>Cd=Zn=Nl>Co=Mn,
while at pH 4.7 it was:

Hg=Fe=Pb=Cu=Al==Cr > Cd > Ni=Zn > Co > Mn.

At pH 5.8. the order was:

Hg=Fe===Pb=Al=Cr=Cu > Cd > Zn > Ni > Co > Mn.

Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were
indications of competition for active sites (CO,H and nhenolic OH rrrouns) on the HA between the
different metals. We were unable to find correlaiions between the affini%es bfthe eleven metals to sorb
on HA and their atomic weights, atomic numbers. valencies, and crystal and hydrated ionic radii. The
sorption of the eleven metals on the HA could be described by the equation Y = lOOi[l +
exp - (A + BX)], where Y = ,, metal removed by HA; X = mg HA; and A and B are empirical
constants

INTRODUCTION Hg(II), Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and
HUMIC XJASTANCES are widely distributed over the Mn. The eleven metals, in dilute aqueous solution,
earths surface. occurring in terrestrial as well as in were allowed to interact with the HA simultaneousl)
aquatic environments. One of the most striking rather than one metal at a time. This procedure was
characteristics of these materials is their relatively thought to resemble more closely what happens in
high content of oxygen-containing functional groups natural soils and waters and also under conditions of
(CO,H. phenolic and alcoholic OH, ketonic and qui- environmental pollution. The results obtained were
nonoid C = 0) through which they can interact with interpreted in the light of current knowledge on
inorganic soil and water constituents. metal-HA interactions.
Humic acid (HA) is that humic fraction that is sol-
uble in dilute base but is coagulated by acidification MATERIALS AND METHODS
of the alkaline extract. In aqueous systems, HA is
normally insoluble at pH < 6.5. The ability of HA to
sorb metals has been demonstrated in a number of The HA was extracted from the surface horizon
(O-15 cm) of the Bainsville clay loam, a Humic Gleysol. on
investigations (SZALAY. 1964: BASU et al., 1964;
the Central Experimental Farm at Ottawa. Ontario. After
CH~WDHURY and BOSE, 1970: RASHID and LEONARD, sampling, the soil was air-dried and ground to pass
1973; RASHID, 1974: BUNZL it al., 1976). Yet much through a 0.25 mm sieve.
remains to be learned about the nature of these inter- The methods used for the extraction of the HA were the
actions. The purpose of this investigation was to same as those described by CHEN &~t al. (1978). Briefly. the
soil was treated with 0.5 N NaOH under N2 for 24 hr at
obtain more detailed information on the sorption of
room temperature. The alkaline extract was acidified with
metals on HA, with special emphasis on effects of pH, 2 N HCI to pH 2 and allowed to stand for 24 hr at room
metal concentration. and HA concentration. We temperature. The coagulate (HA) was separated from the
examined the sorption on HA of the following metals: supernatant (fulvic acid = FA) by centrifugation. The ash
content of the HA was lowered by the following sequence
of procedures: (a) the HA was redissolved in 0.5 N NaOH
* CBRI No. 1139. under N,; the resulting solution was centrtfuged for 20 min
f Visiting scientist from the Institute of Geological at 12,OOOrpm to remove insoluble materials (mainly clay
Sciences. the University of Mainz, Mainz, West Germany. minerals). The clear supernatant was then acidified with
$ Author to whom correspondence should be addressed, 2 N HCI to pH 2 in order to coagulate the HA; (b) the

1701
I702 H. KEKNDORFFand M. SCHNITZLR

Table 1. Analytical characteristics of the HA ion a dry.

ash-free basis) f and H were determined by dry-combustion. N by the
automated Dumas method, S by oxygen-flask combustion
and 0 was calculated by difference. Total acidity Was
',C 53.5 measured by allowing the HA to react with an excess of
SH 6.2 Ba(OH), and back-titrating the unreacted Ba(OH), after
tN 5.5 completion of the reaction. while carboxyl groups were
5 0.8 measured bv the calcium acetate method IS~CINITZER and
%I 34.0 GLIPTA, 196$ Phenoiic hydroxyis were taken as the differ-
meq total acidity/g 6.4 ence between total acidity and CO,H groups.
meq CO:H/g 3.4
Moisture was determined by heating samples at IO.5 C
meq phenolic OH/g 3.0
for 24 hr and ash bv ignition at 75OC lor 4 hr.
pH Measurements were made with the aid of a Fisher
microprobe combination electrode.
partly-purified HA was shaken at room temperature for
12 hr with 100 ml of dilute HF--HCl (5 ml of 52?h
HF + 5 ml of cont. HCI + 990 ml of distilled H,O) solu- RESULTS AND DISCUSSlON
tion. The excess acid xas removed by centrifugation and
washing with distilled H,O. This procedure was repeated
three times in succession: (c) finally. the HA was trans- The freshly coagulated HA was equilibrated with
ferred to dialysis bags and dialyzed for 216 hr against dis- solutions that contained 0.5 x 10-4mol (Fig. la),
tilled H,O changed at frequent intervals. Following these
1.0 x IO- moi (Fig. fb). and 0.5 x 1O~mol (Fig. Ic)
treatments. the HA was freeze-dried. The freeze dried HA
contained -I),, moisture and 0.974;, ash. The latter consisted of each of the eleven met&. The pH was kept con-
mainly of Na, followed by smaller amounts of Cu. Fe and stant at 2.4, while the HA concentration ranged from
Ca. Table I sl~ows;I number of analytical characteristics of 0 to IO00 mg. The volume of each system was 100 ml.
the HA.
Fig. la illustrates the sorption behavior of the eleven
metals from the most concentrated metal solution.
The metals can be subdivided into the following three
A stock solutionwhich was 5 x 10. M in each of the groups: (a) those that were very strongly sorbed by
I1 metals uas prepared from nitrates of Zn. Cd. Hg(II), Cu.
the HA (Fe and Hg); (b) those whose sorption affinity
FetIII). Co. Ni. Mn. Al. Cr(III) and Pb. The stock solution
was diluted with distilled water for the preparation of more was intermediate (Cu. Pb and Al); and (c) metals that
dilute solutions. sorbed weakly on HA under the experimental con-
ditions employed (Ni. Cr, Zn. Mn and Co). As the
metal concentration was lowered (Fig. I b), strong
Required amounts of dry HA were dissolved in 3 ml of sorption of Pb and Cu in addition to Hg and Fe
0.5 N NaOH in SO ml beakers and diluted to 30 mi with coutd be observed. There was a shght reduction in the
distilled HzO. The solutions were acidified with 0.5 N removal of Al but increased sorption of the remaining
HNO, to pH 2 in order to coagulate the HA. The fresh metals in spite of a decrease in the HA weight from
coagulates were transferred to 100 ml volumetric flasks to
1000 to 500 mg. A further reduction of the metal con-
which were added aliauots of metal stock solutions that
were 0.5 x 1W3. I.0 X 10m4 and 0.5 x IO- M in each of centration (Fig. Ic) did not bring about any signih-
the eleven metals. Each solution was diluted with distilled cant changes in the sorption behavior of the metals.
water to 95 ml. the pH adjusted when required with dilute The curve for Al was omitted from Fig. Ic becnuse
NaOH solution and the volume made to lOOmI with dis-
tilled water. Preliminary experiments showed that sorption
concentrations of Al in the supernatants were too low
was essentially complete after shaking at 25 + I C for 2 hr. for reliable measurements,
Thus. a 2 hr equilibration time was adopted. Following
this. each suspension was centrifuged for 30 min at
4000 rpm to separate insoluble residues from the superna-
tams. To aliquots of the clear supernatants. 5 ml of cont. Effects on sorption of raising the pH from 2.4 to
HNO, was added in order to maintain the metals in solu- 5.8. while maintaining a constant metal concentration
tion and further dilutions were made with distilled water.
(0.5 x 10V4 mol of each metal in 100 ml of solution)
Amounts of each metal sorbed were considered to be equai
to the differences between quantities of metals added and
are illustrated in Figs la (pH 2.4). Id (pH 3.7), le
quantities of metals recovered. Each sorption experiment (pH 4.7). and If (pH 5.8). As the pH of the system rose,
uas done in triplicate. The coefficient of variation between greater proportions of added metals were adsorbed by
replicates was 1.9;,. Points in Figs. 1 to 4 are mean values. the HA. At pH 4.7 (Fig. le), 250 mg of HA sorbed
practically all the added Fe. Hg, Pb, Cr, Al and Cu.
while between 10 and 407; of the Mn. Co, Zn, and Ni
All metals were determined on clear supernatants by
was also adsorbed. With further increase m pH to 5.8
atomic absorption spectroscopy. Zn, Cd, Cu, Ni, Co. Fe,
Mn and Pb were determined with the aid of an air-acety- (Fig. If), proportions of the latter elements sorbed
lene flame; A) in a nitrous oxide-acetylene flame and in a increased substantially.
solution containing 2000 ppm of La. For determinations of The sorption data at the four different pH levels are
Zn, Cd and Pb, absorbing and non-absorbing lines as well
summarized in Table 2. The Table also shows data for
as a hydrogen continuum lamp were used. Hg was
measured by nameless atomic absorption spectroscopy as the formation of insoluble metal hydroxides at pH 5.8,
described by MALAIYANDI and BARETTE (1970). Coefficients which were determined in the absence of HA. At the
of variation between replicate metal analyses averaged I>,;, lower pH levels (2.44.7) we did not observe the for-
 Sorption of metals on humic acid 1703

mation of any insoluble hydroxides after allowing the
solutions to stand for 24 hr at room temperature.
From the data in the last vertical column in Table 2
we can attempt to estimate the contributions of in-
soluble metal hydroxides to sorption. Thus, at pH 5.8,
in the cases of Fe. Cu, Cr and to a lesser extent of Al.
Hg and Pb, removal of portions of these metals from
the aqueous systems as hydroxides is possible. To find
out whether the concentrations of metals in our sorp-
tion experiments were of the same order as those
found in polluted sediments, we calculated amounts
of metals sorbed on 1 g of HA from the data in Table
2 and compared these values with data published in
the literature. For example, at pH 4.7. 1 p of HA

Fe

mg HA
Fig. 1. Effects of metal concentration of the equilibrating solution and pH on the sorption of metals on
HA (a) 0.5 x 10m4mol of each metal; (b) 1.0 x 10-5mol of each metal; (c) 0.5 x 10. 5 mol of each
metal; (a) pH 2.4; (d) pH 3.7; (e) pH 4.7; (f) pH 5.8.
1704 H. KERNDORFF and M. SCHNITZER

-*- ..__._ - -0,

l. \,___-o
).. .

Hg Fe Pb Cu Al Ni Cr Cd Zn CO Mn

Fig. 2. Effect of HA concentration on sorption of metals on HA at pH 2.4. Each system contained

0.5 x 10e4 mol of each metal.

PH
Fig. 3. Proportions of metals sorbed by 250 mg of HA at different pH levels. Initial metal content was
0.5 x low4 mol of each metal in 100 ml of solution.
 Sorption of metals on humic acid 1705

0.
. .._ o
Hg Hg,Fe
\ /r

metal cont. moles x lo-

Fig. 4. Proportions of metals sorbed at pH 3.7 from more concentrated metal solutions.

sorbed 1200 pg of Cu, 360 pg of Ni, and 392 fig of Zn. 617776 pg; Ni: 37-728 pg and Zn: 2267,841 pg. Thus,
Concentrations of the same metals in 1 g of fine sedi- the metal concentrations in our experiments were of
ment from the Altrhein river near Mainz, West Ger- magnitudes that were similar to those found in pol-
many (LASKOWSKIet d., 1976) ranged as follows: Cu: luted sediments.

Table 2. Effect of pH on sorption of metals on HA*

pH 2.4 pH 3.7 pH 4.7 pH 5.8 pH 5.8

HA Cm91

Metal 1000 500 200 500 200 250 250 0

% sorption

Hg 80 88 99 98 98 100 98 24**
Fe 88 87 81 96 96 100 100 88**
Pb 65 33 19 96 80 97 98 24**
cu 66 31 12 91 95 97 52**
Al 59 29 7 98 :z 100 100 38**
Ni 5 41 29 61 0
ccdr ;o"
8 3
4' 0 E 7:
7 100 100 53**
41 77 0
Zn 10 5 0 33 8 29 0
co 4 2 0 23 2 22 :z 0
Mn 5 2 0 14 3 13 36 2**

* Each system contained 0.5 x lo- mol of each metal.

** Insoluble hydroxide.
1706 H. KERNDORFF
and M. SCHNITZER

the sum of COzH + phenolic OH groups. was

From the data presented in the previous section, it
appears that the sorption of metals on HA is affected
by the metal concentration, pH of the equilibrating
solution and the amount of HA that is present. To
obtain a better understanding of the sorption pro-
cesses. we replotted some of our experimental data.
Fig. 3 shows the effect of pH on sorption in a system
(100 ml) that contained 250 mg of HA and
0.5 x 1O--4 mol of each metal. The plots indicate that
in general the sorption efficiency increased with
increasing the pH from 2.4 to 5.8. At pH 4.7, and
often more so at pH 5.8, practically all Hg. Fe, Pb,
Cu. Al and Cr was removed from the equilibrating
solution. Similarly, about 75/;; of the Cd, 60% of the
Zn and Ni but only about 40% of the Co and Mn
sorbed on the HA at pH 5.8. Analysis of all sorption
data by the Duncan multiple range test (p = 0.05)
showed that at pH 2.4, the order of sorption was:
tig > Fe > Pb > Cu=AI z Ni > Cr=Zn==Cd=Co=Mn.
At pH 3.7. the order was:
Hg===Fe> Al > Pb > Cu > Cr > Cd=Zn=Ni > Co=Mn,
while at pH 4.7, it was:
Hg===Fe=Pb=Cu=Al=Cr > Cd > Ni=Zn > Co> Mn.
At pII 5.8. the order was:
k(p--=Fe=Pb=Al=Cr=Cu > Cd > Zn r Ni > Co > Mn.
Thus, regardless of pH, Hg and Fe were always most
readily sorbed by HA, while Co and Mn were sorbed
least readily.
The orders of sorption listed above were similar to tion between metal, we examined the sorption of Cu
that reported by BUNZL e? al. (1976) for the selective
uptake of metal ions by hydrogen-saturated peat in Cu, while the other one contained CLI plus the 10
the pH range 3.545, namely, Pb> Cu > Cd=Zn > Ca other metals. The results showed that there was con-
and are in line with observations of RASHID (1974) siderable competition
that sedimentary and peat HAs preferentially adsorb
Cu over Co, Mn, Ni and Zn. The sorption orders also
agree with the findings of CHOWDH~RY and BOSE and the number of active sites was limited.
(1970) who reported that at pH values prevailing
under natural conditions, Pb and Cu were more
strongly retained by soil humus than were Zn, Ni and
CO.
One of the most characteristic features of humic
substances is their relatively high content of oxygen-
~ollt~iiiling fun~tion~~l groups (especially CO,H and
phenolic OH groups) (SCHNITZEK, 1978). It is through
the functional groups that these materials are thought
to interact with metal ions, metal oxides, metal hy-
droxides and minerals to form metal-organic associ-
ations of widely differing chemical and biological sta-
bilities and characteristics, As shown in Table 1, the
HA that was used in this investigation contained per
g 3.4 m-eyuiv of C02H and 3.0 m-equiv of phenolic
OH groups. SO that the total acidity, which is equal to
6.4 m-equivig. This value approximates the concen-
tration of active sites on the HA surface. The HA used
in this investigation contained 5.5/,N (see Table I).
About one half of the latter occurs in proteins, the
remaining one half as ammonia. amino sugars. nucleic
acid bases and possibly in heterocyclic rings. While
some free NH,-groups and cyclic N forms may bind
metals, most workers consider nitrogen-~ontajning
groups in HA to be less active in this respect than
functional groups containing oxygen.
There arc indications in a number of figures of
competition between different metals for active sites
on the HA. The data in Fig. 4 provide such informa-
tion. In this experiment, 1.0 g samples of HA were
equilibrated at pH 3.7 with solutions containing rela-
tively high concentrations of each metal
(5-75 x 10-s mol). As the concentr~~tion of each
metal in the equilibrium solution surpassed
25 x IO- mol. only Hg. Fe, Cr and. to a lesser extent
Al. Pb and Cu. remained sorbed on the HA. No Cd,
Ni. Zn, Co and Mn was sorbed by the HA at this
stage, apparently displaced from the HA by Hg. Fe,
Cr, Al, Pb and Cu. As the equilibrating solution
became more concentrated. Hg. Fe and Cr displaced
Al, Pb and Cu. There are indications in Fig. 4 that at
very high metal ~oncentr~~tion. Fe displaced Cr. Of all
elements investigated, Hg appeared to he retained
most firmly by the HA and could not be displaced
from it by any of the other 10 metals,
Finally, to throw additional light on the competi-
by HA at pH 2.4 from 2 systems: one containing only
between Cu and the other
metals for active sites on the HA. This was especially
so when the systems contained small amounts of HA
Mechanism of sorption
It is apparent from the data presented herein that
the system under investigation is a very complex one.
Eleven different ions plus protons, that is. 12 ions
compete for sorption on the HA. Not only do the 12
ions interact with the HA, but they also mteract with
each other. We attempted to develop a treatment
based on thermodynamics to describe these reactions.
but were unable to do so because of the complexity of
the system. It is for this reason that we are reporting
our results in a less rigorous manner.
Attempts to correlate the affinity of the Ii metals to
sorb on the HA surface with their atomic weights,
atomic numbers, valencies, crystal and hydrated ionic
radii, were unsuccessful. CHOWDHURYand BOSE(1970)
and RASHID (1974) have suggested that the preferen-
tial sorption on HA metals such as Pb and Cu was
 Sorption of metals on humic acid I707

LOGISTICS loo/( I + EXP -_(A+ BX))

A=-2

I JUV 3

Fig. 5. Curves representing the sorption of metals on HA. A is constant. equalling -2

related to the ability of these metals to form stable
complexes, possibly chelates, with HA. More recently,
different views have been expressed. GAMBLE et al.
(1976) have shown by NMR measurements that
Mn(II) forms an outer sphere complex with fulvic
acid. while Fe(III) forms an inner sphere complex
with the same material. Similarly, GAMBLE et al.
(1977) and MCBRIDE (1978) concluded from ESR
measurements that Mn(I1). rather than forming che-
lates with humic materials, was bound in fully hyd-
rated form [as Mn(H,O)i] by electrostatic bonding
only. An outer sphere complex is one in which the ion
is bound electrostatically to the polyanion (such as
HA) without displacement of water of coordination
from the ion by a negatively charged functional
group. In an inner sphere complex, by contrast, ligand
functional groups may enter into coordination pos-
itions and displace strongly coordinated H,O mol-
ecules. MCBRIDE (1978) concluded from ESR investi-
gations that HA does not form highly covalent metal-
organic bonds with Cu nor with Mn. He believes that
a single electrostatic bond formed between the HA
and metals is consistent with the ESR results, which
appears to put some doubt on chelation as a pre-
dominant mechanism.
Regardless of which mechanism is the more rele-
vant one, our data show significant differences in the
sorption of the 11 metals on HA. depending on the
pH, metal and HA concentration.
Modrls,f&r the sorptim qf metals on HA
By curve fitting a family of curves was drawn from
the experimental data to model the sorption of metals
on HA (Fig. 5). The equation for these curves, calcu-
lated on the computer, is:
Y = lOO,![l + exp - (A + SX)] (11
where:
Y = % metal sorbed by HA
X=mgHA
A and B = empirical constants
Effects of varying constants B and A arc shown in
Fig. 5. If A and B are high, the slopes are steep and
the curves are close to the ordinate (curves V. U. T. S
and R). But if A and B are low, the curve is less steep
and is far from the ordinate (curve N). Medium values
for A and B yield curves Q. P and 0.
Curves V to R in Fig. 5 are representative of the
sorption on HA of Fe. Hg. Cr and AI (See Fig. le),
curves Q to 0 of the sorption of Pb and Cu and curve
N of the sorption of Cd, Ni. Zn, Co and Mn.
If the pH of the system increases, the slopes in-
crease because of rapid increases of B. while A
changes little or decreases.
If the metal concentration increases. B tends to
remain almost constant while A tends to decrease
slightly, so that the slope of the curves changes little.
.4~knorv(ed~r,tfrrlts- -We thank B. ZAUWK for technlcal as-
sistance, K. PKI(I.L of the Engineering and Statistical
Research institute for statistical analyses and the German
Academic Exchange Service (DAAD) for financial assist-
ance to H.K.
1708 H. KEREDORFF and M. SCHNIPZW

REFERENCES and TOBS~HALL H. I. (1976) Abundance and distribution

of some heavy metals in recent sediments of a highly
polluted limnlc-fluviatile ecosystem near Mainz, West
BASI: A. N., MUKHERJEE D. C. and MUKHERJEE S. K. (1964) Germany. In Ellrironmrnral Biogeochc~n~r.srr~. (ed. J. 0.
Interaction between humic acid fraction of soil and trace Nriagu). Vol. 2, pp. 5X7- 595. Ann Arbor.
element cations. J. Iudiun Sot. Soil Sci. 12, 31 I-318. MALAIYASIX M. and BARET~L J. (1970) Determination of
BU&;ZL K.. SCHMIDT W. and SANSONI B. (1976) Kinetics of submicro-quantities of mercury m biological materials.
ion exchange in soil organic matter IV. Adsorption and A,1trl. Lelr. 3, 579 5x4.
desorption of Pb, Cu+. Cd. Zn* and Ca+ by M~BRII~I M. B. (1978) Transition metal bondmg in humic
peat. J. Soil SC;. 27. 32~ 41. acid. An ESR study. Soil Sci. 126. ?0&209.
CHEN Y., SE.N~SI N. and S~HYXITZERM. (1978) Chemical RASHII) M. A. (1974) Absorption of metals on sedimentary
and physical characteristics of humic and fulvlc acids and peat humic acids. Chrrn Geol. 13, I 15- 123.
extracted from soils of the Mediterranean region. Gro- R4SHID M. A. and LtO~uAKIIJ. D. (1973) Modifications of
dc>rnlu 20, 87FlO4. the solubllity and precipitation behaviour of various
CHOWDHLIRY A. N. and BOSE B. B. (1970) Role of humus metals as a result of their interactions with sedimentar)
matter in the formation of geochemical anomalies. Proc. humic acid. Cheln. Geoi. 11. X9-97.
3rd IN. Geochm~. Erplor. Synp.. Toronto, pp. 41&413. STHNITZF.R M. (1978) Humic substances: Chemistry and
GAMBLE D. S.. LAUGFORI) C. H. and TONG J. P. K. (1976) reactions. In Soil Orymic Mtrrrw. (eds M. Schnitzer and
The structure and equilibria of a manganese (11) complex S. U. Khan), pp. I 64. Elsevier.
of fulvic acid studied by ion exchange and nuclear mag- SCHXTLER M. and GUPTA U. C. (1965) Determination of
netlc resonance. CU,I. J. Cllem. 54, 1239~1245. acidity in soil organic matter. SOI/ SC,;. Sot. Am. Proc,. 29,
GAMHLE D. S.. SCHNITZER M. and SKINNER D. S. (1977) 274~ 277.
Mn(II)-fulvic acid complexing equilibrium measurements SZALAV A. (1964) Cation exchange propertlcs of humic
by electron spin resonance spectrometry. Crr~t.J. Soil SC;. acids and their importance in the geochemical enrich-
57. 47 53. ment of UOS _ and other cations. G~&~ir,l. Cosmochim
LASI(OWSKI N.. KOST T. H.. POMMERFNKE K.. SWAFEH A. Actu 28, 160.5 1614.