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Journal of Colloid and Interface Science 270 (2004) 4755

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Cu(II) retention on a humic substance


R.A. Alvarez-Puebla,a C. Valenzuela-Calahorro,b and J.J. Garrido a,
a Department of Applied Chemistry, Public University of Navarra, Campus Arrosada, E-31006 Pamplona, Spain
b Department of Inorganic Chemistry, Faculty of Pharmacy, University of Granada, E-18071 Granada, Spain

Received 11 February 2003; accepted 26 August 2003

Abstract
Humic substances (HS) are macromolecular products derived from a physical, chemical, and microbiological process called humification. These substances play an important role in the mobility and bioavailability of nutrients and contaminants in the environment.
Adsorption isotherms provide a macroscopic view of the retention phenomena. However, complementary techniques are needed in order
to study the retention mechanism. The application of the classical models and some modern ones, based on humic substances chemistry, do
not accurately describe these adsorption data. The aim of this paper is to model isotherms and combine adsorption data with spectroscopy
and microscopy techniques to study the Cu(II) retention on a HS. The adsorption isotherms shape varies significantly with the solution pH
from L-type (pH 26) to S-type (pH 8). FTIR shows that, when pH is 2 the retention of Cu(II), as [Cu(H2 O)6 ]2+ , is the preferred retention
mechanism. The quantity of Cu(II) retained as [Cu(OH)(H2 O)6 ]+ rises, as pH increases. At pH 4, Cu(II) begins to precipitate, which is the
preferred mechanism at pH 8.02. The presence of HS has a great influence on the precipitation process of Cu(II), giving rise to amorphous
precipitates. As it is shown by SEM-XRF, Cu(II) distributes heterogeneously on HS surface and accumulates on the humic phases. The
presence of different anions (chloride and nitrate) slightly modifies the HS behavior as cation exchanger. When Cl ions are present, part
of the Cu(II) form [CuCl4 ]2 , which is stable in solution due to its negative charge; when the anion present is NO
3 the formed complex,
[CuNO3 ]+ , is retained on the HS.
2003 Elsevier Inc. All rights reserved.
Keywords: Adsorption; Humic substance; Isotherms; Cu(II); FTIR; SEM

1. Introduction
The common definitions for humic substances (HS) and
their fractions are ambiguous and, in some instances, arbitrary [1]. However, it could be said that they are macromolecular products derived from a physical, chemical, and
microbiological process called humification of organic
molecules from plants, animals, microorganism tissues, and
metabolic products. The HS are the most widespread natural nonliving organic materials in all terrestrial and aquatic
environments, up to 80% of soil organic matter and up to
60% of dissolved organic carbon [2]. Based upon their solubility in acids and alkalis, HS can be fractioned into humic
acids (HA), fulvic acids (FA) and humin. The HA can be divided into brown humic acids (BHA) and gray humic acids
(GHA) [3]. Due to their colloidal and polyfunctional charac* Corresponding author.

E-mail address: j.garrido@unavarra.es (J.J. Garrido).


0021-9797/$ see front matter 2003 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2003.08.068

ter, these substances play an important role in the mobility


and bioavailability of nutrients and contaminants in the environment [4]. One of the main features of HS in the environment is their capacity to interact with metal ions to
form soluble complexes, colloidal substances, and/or insoluble substances [3]. The interactions between HS and metals
have great interest from chemical, biological, and environmental perspectives, due to the capacity of HS to complex
metal ions. The study of interactions between HS and metal
ions requires the characterization of both. The chemical behavior of transition metals is well known [5]. The behavior
of humic substances is scarcely known, despite their physical and chemical similitudes, as a consequence of their
fractal nature [6]. Elemental analysis is probably the most
frequent tool used in the characterization of HS. This technique provides information about the distribution of major
elements and is useful to distinguish different fractions of
HS [2]. Carboxyl and phenolic groups are the main acidic
groups. The determination of such groups in HS is closely
connected with the retention of metal ions.

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R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

Adsorption isotherms provide helpful information about


the retention capacity and the strength with which the adsorbate is held on the adsorbent [7]. To date, only a few
reports on using adsorption isotherms in the study of some
transition metal ions on HS have been made [810]. The
retention process has been studied using the classical Langmuir, Freundlich, or Tth models and other more refined
and modern ones that use the double diffuse layer theory,
such as Model V by Tipping and Hurley [11], NICA and
NICADonnan by Kinniburgh et al. [12], Stockholm by
Gustafsson [13], or the Liu and Gonzalez model [9]. The
classical models do not adequately fit the experimental data,
whereas modern ones need the knowledge of a great number
of variables, some of which are difficult to determine experimentally. These models are usually based on the HS surface
chemistry.
The adsorption isotherms analysis is useful to study
the retention process [7], because it provides a macroscopic view of the retention phenomena. Thus, complementary techniques are needed to study the different retention process [14]. In line with that, many techniques have
been employed to study interactions between HS and metal
ions, as reviewed by Senesi [15] and Schulten and Leinweber [16]. Infrared spectroscopy has also been widely used to
study the retention of some metal ions on several HS [17,18].
The aim of this work is to model isotherms and combine
adsorption data with spectroscopy and microscopy techniques in order to study the Cu(II) retention on a HS. This
global aim may be outlined as follows: (a) measurement of
Cu(II) adsorption isotherms on HS; (b) development of a theoretical model to fit in to the experimental data, considering
the chemistry of Cu(II) in aqueous solution and the global
adsorption as the sum of several single processes; and (c)
characterization of the retention process using FTIR, XRD,
XRF and SEM.

2. Experimental methods

Table 1
Physical and chemical characteristics of the humic substance
Fraction percentage
FA
BHA
GHA
Humin

2.8
27.1
60.9
9.2
Qa , M b , K c

Main minerals
Cd
Hd
Nd
Sd
Sie
Ale
Fee
Ke
Cae

Elemental analysis in percentage by weight


47.9
4.91
0.67
1.18
2.15
0.80
0.86
0.24
2.99

Surface area
As N2 (77 K)/m2 g1 (DRK)
As CO2 (273 K)/m2 g1 (DRK)

<1
42.5

Acidbase properties
pH (NaCl 0.05 M; 298 K)
4.02
C strong acid groups /mol kg1
C weak acid groups /mol kg1
2.95

5.77
pKA
pKB

a
b
c
d
e

3.92
8.22

-Quartz.
Muscovite-M1.
Kaolinite-Md.
CHNS.
XRF.

of the strong acidic groups. The acidbase constants were estimated from the end points obtained from a potentiometric
acidbase titration in a Metrohm Titrino 702SM autoburette
according to Santos et al. [21]. The results of the characterization of the Fluka HA are listed below in Tables 1 and 2.
Solubility as a function of the solution pH (Fig. 1) was calculated using a gravimetric method according to Franson et
al. [22].
2.2. Adsorption isotherms

2.1. Materials
The adsorbent used in this study was a commercial
HS (Fluka Chemical Co). HS characterization included (a)
humic substance partition as a function of pH using the
method proposed by the International Humic Substances
Society [19]; (b) chemical composition using a Carlo Erba
EA 1108 elemental analyzer and a Link Analytical Pentaler
EXL-10; (c) mineralogical composition of the inorganic
fraction by X-ray diffractometry (Siemens D500); (d) scanning electronic microscopy (JEOL JSM 6400 mod. 6210);
and (e) porous texture by N2 (77 K) and CO2 (273 K) adsorption measured with a Micromeritics 2010 by static volumetry [20]. The strong acidic groups and the total acidity of
HS were determined by calcium acetate and barium hydroxide methods [3], respectively. The weak acidic groups were
calculated as the difference between the total acidity and that

Batch adsorption was carried out using 50 cm3 scaled


centrifuge tubes made out of low-density polyethylene. Samples of HS 0.2500 0.0005 g were suspended in 20 cm3 of
MilliQ-distilled water. The pH was adjusted by the addition
of diluted HCl or NaOH. Suspensions were then placed in a
thermostated water bath, Grant OPLS 200, at 298.0 0.2 K
for 24 h. The required amount of copper (0, 10, 20, 40, 80,
120, 160, 320, 640, and 1280 mmol kg1 ) was added to
every sample from a 10,000-ppm solution of CuCl2 6H2 O
(Merck, analytical grade), and the ionic strength adjusted to
0.05 M with NaCl 0.25 M solution. The volume was set to
25 cm3 and the pH readjusted. Samples were then placed
in the thermostated water bath for 24 h, time enough to
reach thermodynamic equilibrium, centrifuged for 30 min
at 14,000 g (Sigma, Mod. 2-16), and filtered (Millipore,
0.45 m). The Cu(II) concentration in filtrates was deter-

R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

Table 2
X-ray fluorescence microanalysis from several spots on HSCu system surface
% (w/w)
Spot 1

Spot 2

Spot 3

Initial concentration of Cu(II) in mmol kg1


0

320

640

1280

33.7

34.6

0.57
25.9

a
a
a
a
a

a
a
a
a
a

0.69
27.6
0.68
0.61

S
Si
Fe
Al
K
Ca
Cu

0.97
1.67
1.09
1.08
0.32
2.87

S
Si
Fe
Al
K
Ca
Cu

S
Si
Fe
Al
K
Ca
Cu

a
a
a

0.93
0.32

0.30
0.51

0.97
1.67
1.72
1.08
0.32
1.87
1.21

1.48
1.91
2.29
1.01

1.13
1.69
1.82
1.11
0.35
2.34
0.63

1.19
0.75
0.90
0.73

0.91
0.81
0.90
0.77

0.86
0.91
0.92
0.84

1.18
0.75
1.06
0.73

0.88

1.04
1.12

0.68
1.81

0.88
2.23

1.95
1.62

a Not detected.

2.3. FTIR spectroscopy and SEM


Selected samples of the isotherms (doped with 0, 80, and
1280 mmol of Cu(II) per kg of HS), washed three times with
ethanol during 5 min, vacuum-filtered, and dried at 333 K
under vacuum for 24 h, were characterized with transmission
FTIR (Nicolet, Avatar 360) on pressed KBr pellets (150 mg
KBr and 1 mg of sample). The transmission FTIR cell was
flushed with N2 gas for 10 min before scanning to remove
atmospheric water vapor and CO2 from the spectrophotometer. The spectral resolution was set to 1 cm1 and 150 scans
were collected in each spectrum. XRD (Siemens, D500) was
recorded in the samples where FTIR showed the existence of
a copper inorganic phase. Micrographs of the HACu system were obtained by SEM on pressed pellets using a JEOL
JSM 6400 Mod. 6210 microscope equipped with an EDAX
system (EXL-10) from Link Analytical Pentaler.

3. Theoretical
The following equilibrium equations for copper as a function of pH have been assumed (in all the cases it has been
assumed that Cu2+ has a coordination number of 6 and its
structure has the tetragonal distortion due to the JahnTeller
effect) [5]:
2+
+


+ OH  Cu(OH)(H2O)5 + H2 O, (1)
Cu(H2 O)6

+
2+
1
Cu(OH)(H2O)5  (H2 O)4 Cu(OH)2 Cu(H2 O)4
2
(2)
+ H2 O,
2+
1
(H2 O)4 Cu(OH)2 Cu(H2 O)4
+ OH
2


 Cu(OH)2 (H2 O)4 ,
(3)





Cu(OH)2 (H2 O)4 + OH  Cu(OH)3 (H2 O)3




Fig. 1. Variation of the humic substance DOM percentage as a function of


pH.

mined by atomic absorption spectrophotometry (Perkin


Elmer, Mod. 2100) and the amount of Cu(II) retained was
calculated from the difference between the initial amount
and the equilibrium concentration. The residue was vacuumdried at 338 K.
To test the influence of ionic strength, a new isotherm at
pH 2 was obtained under similar conditions except that Cu
was added from 10,000-ppm solution of Cu(NO3 )2 (Merck,
analytical grade); and ionic strength and pH were adjusted
with 0.25 M NaNO3 and dilute HNO3 solutions.
The isotherm at pH 2 was replicated five times, to test
the reproducibility of adsorption data. In all cases, the error
percentage was less than 1.7%.

49

Cu(OH)3 (H2 O)3

+ H2 O,
2

+ OH  Cu(OH)4 (H2 O)2

(4)

+ H2 O.

(5)
]2+

and
In this paper [(H2 O)4 Cu(HO)2 Cu(H2 O)4
[Cu(OH)(H2O)5 ]+ have been considered equivalent species.
In the same way, [Cu(OH)2(H2 O)4 ] corresponds to the hydroxide Cu(OH)2 , which will be found mainly as a precipitated solid [23].
The retention of a metal ion on a HS could be described with a model that assumes different binding mechanisms [24,25]. In the experimental conditions described
above, one, two, and even three different simple retention
processes can take place:
Process 1. Adsorption of the cation [Cu(H2 O)6 ]2+

2+ 

2 S-H + Cu(H2 O)6
 S2 Cu(H2 O)4 + 2H3 O+ . (6)
Process 2. Adsorption of the cation [Cu(OH)(H2O)5 ]+
+ 


S-H + Cu(OH)(H2O)5  SCu(OH)(H2O)5 + H3 O+ .
(7)

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R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

Process 3. Precipitation of Cu(OH)2 on the solid surface


2+
+ 2OH  Cu(OH)2 .
Cu(H2 O)6
(8)
The adsorption processes usually fit into kinetic laws such

as
dC
= ka C n (1 ) kd ,
(9)
dt
where ka and kd are the adsorption and desorption rate coefficients, respectively; is the coverage surface fraction; and
n is the partial order of the process [26,27].
In the equilibrium, Eq. (9) easily leads to

KC n
ns
= =
.
s
nm
1 + KC n

(10)

When n = 1 (Langmuir equation conditions),


ns =

Knsm C
,
1 + KC

(11)

where ns are the moles of Cu(II) adsorbed per mass unit of


HS; nsm is the retention capacity of HS for Cu(II); and K is
the kinetic equilibrium constant.
When the single experimental adsorption isotherms have
a final segment of high slope it could be attributed to a simple
multilayer process or, as in this case, to precipitation on the
surfaces of low solubility species. The kinetic law can be
expressed using the equation
dC
= k1 C b k2 ns
dt
which, at equilibrium, leads to

(12)

ns = (k1 /k2 )C b = AC b .

(13)

In the most general case, the adsorption global process


consists of the three single processes indicated by Eqs. (6),
(7), and (8). The experimental isotherms will fit into the next
general equilibrium equation,
ns = ns1 + ns2 + ns3
K1 nsm(1) C K2 nsm(2) C
+
+ AC b ,
=
1 + K1 C
1 + K2 C

(14)

where ns1 and ns2 are the moles of Cu(II) adsorbed per gram
of HS as [Cu(H2 O)6 ]2+ , [Cu(OH)(H2O)5 ]+ , respectively,
and ns3 the moles of Cu(II) precipitated as Cu(OH)2 on the
HS surface.

4. Results and discussion


4.1. Characterization of the commercial humic acid
Table 1 shows the results for the humic substance partitioning, elemental analysis, surface area, and acidic groups.
The main fractions are humic acids (88%), corresponding to
BHA (27.1%) and GHA (60.9%). Fulvic acids and humin

are minor components, 2.8% and 9.2%, respectively. Elemental analysis also shows the presence of inorganic elements (Si, Al, Fe, Ca, and K), indicative of the presence
of mineral phases. The mineral phases were identified by
XRD and FTIR spectroscopy on the humin fraction because it is the fraction richest in inorganic compounds.
The X-ray diffractogram showed -quartz (2 = 26.7,
20.9, 50.2 ) to be the main component of the crystalline
phase, whereas kaolinite-Md (2 = 12.5, 25.0, 38.7 ) and
muscovite-M1 (2 = 8.8 , 26.5 , 19.8 ) were minor components. On the other hand, FTIR spectra [28] exhibited the
presence of (a) -quartz, doublet band at 797 and 778 cm1 ;
(b) kaolinite-Md, two sharp peaks at 3695 and 3619 cm1 ,
assigned to two of the four OH characteristic tensions
of this clay, and a small weak band at 694 cm1 ; and
(c) muscovite-M1, characterized by a shoulder at 915 cm1
and a weak peak at 469 cm1 . The bands between 1165 and
1033 cm1 are assigned to SiO tensions due to both quartz
and clays, whereas the band at 533 cm1 was the result of
the typical SiOAl deformation in clays.
The HS porous texture has been studied using adsorption isotherms of N2 (77 K) and CO2 (273 K) (Table 1).
The molecular size of both adsorbates is similar (0.30 and
0.33 nm, respectively); however, the sample adsorbed CO2
but no N2 was retained, which can be explained by the highly
narrow microporosity of this kind of material. Whereas CO2
can penetrate into the micropores, N2 cannot, due to diffusion restrictions because of its lower kinetic energy at
77 K [29,30].
The HS titration curve had two equivalence points (Table 1) corresponding to two acidic group families: carboxylic (pKA = 3.92) and phenolic (pKB = 8.22) acidic
groups. The concentration of carboxylic acidic group was
greater (4.02 mol kg1 ) than that of phenolic acidic group
(2.95 mol kg1 ). These values were in agreement with the
bibliography for HS [2].
The dissolved organic matter (DOM) percentage (Fig. 1)
was practically constant in the pH range 24, first increasing
slightly from pH 4 to 6 and then abruptly from pH 6 upward.
Since the sample is a HS, composed of different fractions
(FA, BHA, GHA, and humin), the DOM percentage in the
first segment is the result of the FA dissolution, which is soluble at any pH value [3]. As the pH increases, so does the
negative charge, due to the continuum ionization of acidic
groups and hence the solubility.
The SEM micrograph of HS (Fig. 2a) shows a heterogeneous surface where white particles are immersed into a gray
phase that produces distinct color tones. The X-ray fluorescence microanalysis performed on the micrograph marked
spots (Fig. 2a; Table 2) is in agreement with the heterogeneous distribution of the mineral phases. Silicon is the only
element detected in the white particles (spot 1). The percentage of Si, Al, and Fe is slightly greater in the light gray
phases (spot 2) than in the dark gray ones (spot 3) suggesting that while quartz is free, not bonded to HS, the clays are
immersed in the organic matrix, bonded to HS.

R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

51

Fig. 2. SEM micrographs of humic substance. SEM micrographs of the residues of selected points, (a) 0, (b) 320, (c) 640, and (d) 1280 mmol kg1 , from
the sorption isotherms at pH 2 of Cu(II) on a humic substance (I = 0.05 M NaCl; 298 K). (The results of the XRF analysis on the marked spots are listed in
Table 2.)

4.2. Copper adsorption isotherms on HS


The shape of the isotherms and the amount of Cu(II)
retained varied with pH (Fig. 3). According to the Giles classification [31], the isotherms can be included in the L-type,
except for the isotherm at pH 8.02, which was S-type. At
this pH, the slope of the isotherm was zero for equilibrium
concentrations less than 1 mM. From pH 2.06 to 3.2 the adsorption isotherms can be classified as L-1 type, and at 4.11
and 6.13, the isotherms were L-3 type.
The lineal model shows R 2 > 0.95, but due to the narrow
application range (040 mmol kg1 ), describes only a part
of the retention process. The Freundlich model fits well too;
nevertheless, the fit of a set of data to a power law is too general, so it gives little information about the retention process.
The adsorption isotherms (Fig. 3) did not fit adequately to
the Langmuir equation, which suggests that the experimental
system did not follow the reversibility and kinetic conditions
of the Langmuir equation, or that the global process is composed of more than one single process, in agreement with
the stability diagrams for the different species of Cu(II) in
aqueous solution as a function of pH and Cu(II) concentration [23].
The global process that occurs in the experimental
isotherms seems to be formed by two single processes, so
Eq. (14) reduces to the following:

Fig. 3. Adsorption isotherms at pH constant of Cu(II) on a humic substance


(I = 0.05 M NaCl; 298 K).

At 2.06  pH  3.2, two simultaneous single processes


take place, adsorption of [Cu(H2O)6 ]2+ and [Cu(H2O)5
(OH)]+ :
ns = ns1 + ns2 =

K1 nsm(1) C

K2 nsm(2) C

.
(15)
1 + K1 C
1 + K2 C
At pH 4.11 and 6.13, two simultaneous processes take
place, adsorption of [Cu(H2 O)5 (OH)]+ and precipitation of

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R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

Cu(OH)2 on HS surface:
ns = ns2 + ns3 =

K2 nsm(2) C
1 + K2 C

+ AC b .

(16)

At pH = 8.02, a single precipitation process of Cu(OH)2


takes places:
ns = ns3 = AC b .

(17)

The experimental data (ns vs C) fit very well to Eqs. (15),


(16), or (17), to give the results shown in Table 3, as indicated by R 2 values (continuous lines in Fig. 3). This model
reveals a great selectivity of the HS to adsorb the different
Cu(II) species. The selectivity depends on pH and adsorptive concentration.
Fig. 4 shows the distribution of the amount of copper
species adsorbed as a function of C0 , for processes (15),

Table 3
Fitted parameters for Eqs. (15), (16), and (17)
pH

nsm(1)
(mmol kg1 )

K1

nsm(2)
(mmol kg1 )

K2

2.06
2.51
3.20
4.11
6.13
8.02

171
160
171

2.97
3.30
3.42

490
439
1635
1.91 103
5.56 103

0.08
0.21
0.22
0.30
4.70 102

2.10
2.33
20.4

R2

11.3
8.03
1.77

0.9993
0.9997
0.9994
0.9997
0.9992
0.9948

Fig. 4. Surface speciation of Cu retention on HS at pH of (a) 2.06, (b) 2.51, (c) 3.20, (d) 4.11, (e) 6.13, and (f) 8.02, as a function of initial metal concentration,
obtained applying Eqs. (15), (16), and (17).

R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

(16), and (17), calculated using the parameters shown in Table 3. Between pH 2.51 and 3.20 (Figs. 4a4c) there is an
intersection point in the curves of the amount of species adsorbed. This intersection decreases as pH increases due to
the increase in the concentration of OH ions. When C0
was below this point, Cu(II) was preferably adsorbed as
Cu(H2 O)6 ]2+ .
At pH 4.11 (Fig. 4d) most of the strong carboxylic acidic
groups are ionized, increasing the surface charge and the
amount of adsorbed metal at low C0 . The increase of the
OH concentration determines that Cu adsorption is higher
as [Cu(H2 O)5 (OH)]+ than [Cu(H2 O)6 ]2+ . The adsorbed
[Cu(H2 O)5 (OH)]+ probably promotes the precipitation of
Cu in unsaturated conditions (pKsp Cu(OH)2 = 19.1), which
behaves as precipitation micronuclei for Cu(OH)2 growth, in
accordance with the surface precipitation model, where the
interface is a mixing zone for the ions of the new solid phase
and those of the substrate [32].
From pH 6.13 the DOM percentage (Fig. 1) rises, causing a competition between the bulk HS and the dissolved HS
for the Cu ions. The net effect is the shift of the precipitation
edge to higher C0 with pH. At pH 6 (Fig. 4e), the adsorption [Cu(H2 O)5 (OH)]+ was higher than the precipitation of
Cu(OH)2 for C0 < 1100 mmol kg1 . At pH 8 (Fig. 4f), the
preferred retention mechanism was the precipitation. The inhibition of the adsorption of aquacomplex ions by bulk HS
and the shift of the precipitation edge show that the dissolved
HS forms very stable complexes with Cu(II).
The FTIR spectra at several selected points (0, 80, and
1280 mmol kg1 Cu) of the adsorption isotherms at pH 2,
4, 6, and 8 are presented in Fig. 5. They give reasonable
support to the results obtained in the application of the model
(Eq. (14)). All the spectra exhibit bands from the mineral
phases (quartz, muscovite and kaolinite), which enlarge their
intensity as pH increases due to the HS dissolution.
At pH 2 (Fig. 5a), the Cu(II) is adsorbed as [Cu
(H2 O)6 ]2+ , as shown by the increased intensity of the
bands: (a) 3420 cm1 , due to OH stretching (OH); (b)
1600 cm1 , due to HOH deformation (OH); and (c)
525 cm1 , due to CuO stretching [33]. The OH stretching (3420 cm1 ) and the asymmetric and symmetric
COO stretchings (1610 and 1380 cm1 ) increase with
metal concentration, while the OH stretching of H-bonded
COOH (2500 cm1 ) [10], the C=O stretching of COOH
(1710 cm1 ), and the CO stretching and OH deformation decrease (1240 cm1 ). So, at pH 2 (Fig. 5a),
[Cu(H2 O)6 ]2+ is the predominant adsorbed Cu(II) species;
the formation of Cu(II) mixed complexes with water and HS
functional groups is suggested by the reduction of the intensity in the broad shoulder of OH stretching of H-bonded,
C=O stretching and CO stretching and OH deformation
of COOH, and the increase of asymmetric and symmetric
COO stretchings as metal concentration increased [10,17].
For pH 4.11 (Fig. 5b), the increase of asymmetric and
symmetric COO stretchings and the reduction of the OH
stretching of H-bonded, C=O stretching and CO stretching

53

Fig. 5. FTIR spectra of the residues of selected points (C0 = 0, 80, and
1280 mmol kg1 ) from the sorption isotherms at constant pH of Cu(II) on
a humic substance (I = 0.05 M NaCl, 298 K). (a) pH 2.06, (b) pH 4.11, (c)
pH 6.13, and (d) pH 8.02. The spectra of [Cu(H2 O)6 ]Cl2 and Cu(OH)2 are
also included.

and OH deformation in COOH suggest that the formation of complexes with carboxylic acid groups is the preferred adsorption mechanism. The increase in the amount
adsorbed compared to that at pH 2 is due to the smaller
competition between Cu(II) and H+ for the adsorption
sites in HS [34] and to the presence of the highly reactive [Cu(OH)(H2O)5 ]+ . However, some authors have suggested that the adsorption phenomena at low pH can also be
due to the formation of complexes between Cu(II) and carbonyl [35] or nitrogen-containing groups from the HS [36].
The complexation with carbonyl groups cannot be confirmed
by FTIR because their bands overlap with the bands due
to the C=O group of COOH (1710 cm1 ), asymmetric COO stretching (1610 cm1 ), and (OH) of water
in [Cu(H2 O)6 ]2+ . Complexation with N-containing groups
could not be confirmed either. We did not find bands arising from these groups or metalN-containing groups, in

54

R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

agreement with Evangelou et al. [37], probably because


the signals NH vibrations, 1920 cm1 , and amide bands,
1644 cm1 , overlapped other absorption bands, so that, their
existence cannot be disregarded.
At pH 6 (Fig. 5c), Cu(II) forms a hydroxide, as revealed by the three strong sharp peaks (3445, 3357, and
3316 cm1 ), particularly that at 3360 cm1 , assigned to
OH stretching from copper hydroxides such as Cu(OH)2 ,
and a medium band (1614 cm1 ), appearing as a sharp peak
at 16301635 cm1 , assigned to OH deformation in hydroxyl groups [38]. In the CuHS system, the OH stretching rises slightly when C0 = 80 mmol kg1 and strongly
when C0 = 1280 mmol kg1 . At C0 = 1280 mmol kg1 ,
this band shows a shoulder (3363 cm1 ) that could be the
OH stretching corresponding to the Cu(OH)2 precipitate.
The bands assigned to asymmetric and symmetric COO
stretchings (1610 and 1380 cm1 ) increase with metal
concentration. In the signal at 1610 cm1 a weak sharp
peak at 1630 cm1 that rises with metal concentration can be
seen. This band seems to be due to OH deformation for the
hydroxyl groups of the hydroxide. The C=O stretching of
COOH (1710 cm1 ) and the CO stretching and OH deformation (1240 cm1 ) do not show a great variation, unlike the OH stretching of H-bonded COOH (2500 cm1 ),
which fades to disappearance as metal concentration rises.
These changes suggest a combination of mechanisms in
the retention process. At C0 = 80 mmol kg1 , Cu(II) retention forming complexes with carboxylic acid groups is
the preferred adsorption mechanism, according to Alcacio
et al. [39]; however, at C0 = 80 mmol kg1 , the spectra exhibit bands due to copper hydroxide (shoulder at 3363, and
a sharp peak at 1631 cm1 ), suggesting that, at this metal
concentration, the precipitation of copper is an important retention mechanism.
At pH 8 (Fig. 5d), at high copper concentrations the bands
due to copper hydroxide (3363 and 1633 cm1 ) and OH
stretching clearly rose, suggesting the formation of an amorphous copper hydroxide, although Cu(OH)2 crystal phases
were not detected by XRD, because the crystals were not of
sufficient size.
The SEM micrographs obtained for samples corresponding to C0 = 320, 640, and 1280 mmol kg1 , from the
isotherm at pH 2, are presented in Figs. 2b and 2c. Table 2 shows the XRF results for the marked spots in the
micrographs. XRF shows different distribution of adsorbed
Cu(II) on the HS surface. In the white phase (spot 1), mainly
formed by quartz, Cu(II) adsorption is only detected at high
metal concentration. Since this phase has a low surface area
and due to the size and penetration capacity of the X-ray
beam, it is likely that the small amount of copper detected
might be a consequence of the complexation to HS that is
enclosing the mineral. The light gray phase (spot 2), formed
by HS and clays, adsorbs copper in all the range of concentration but to a lower extent than the dark gray phase (spot 3),
which is formed only by HS. Despite HS having many surface functional groups, the medium retention in the humic-

clay system (spot 2) can be explained because some of them


are occupied cleaving the HS to the clay surface [40].
4.3. Copper adsorption on HS as a function of
ionic strength
Fig. 6a shows the adsorption isotherms (298 K) for copper at pH 2 and ionic strength 0.05 M in NaCl and NaNO3 .
Both isotherms have similar shapes and, according to Giles,
can be classified as L-1. At low concentrations, copper adsorption is similar. However, from C0 = 220 mmol kg1 upward the retention in the isotherm with NaNO3 as electrolyte
is larger than that with NaCl. This fact can be explained
because copper has a greater tendency to form complexes
with chloride than with nitrate [5]. The stability of the complexes formed with chloride, [CuCl4 ]2 , partially inhibits
the retention on HS due to their negative charge. Comparison between FTIR spectra for samples corresponding to
C0 = 320, 640, and 1280 mmol kg1 from isotherm with
nitrate (Fig. 6b) with those obtained for the isotherm with
chloride (Fig. 5a) show that the nitrateHS system FTIR exhibits a strong sharp peak at 1384 cm1 , assigned to the
asymmetric stretching (E
) of the D3h nitrate anion [33].
As copper retention increases the symmetry species E
loses
its degeneration, giving rise to another two active IR peaks,

Fig. 6. (a) Adsorption isotherms (298 K) at pH 2 of Cu(II) on a humic substance with 0.05 M different nature ionic strength, NaCl and
NaNO3 . (b) FTIR spectra of the residues at selected points (0, 320, and
1280 mmol kg1 ) from the adsorption isotherms at pH 2 of Cu with ionic
strength of NaNO3 .

R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755

1423 cm1 (B2 ) and 1355 cm1 (A1 ), suggesting the lose
of symmetry from the D3h to the C2v point group [41]. The
strong and sharp peak due to asymmetric nitrate stretching
(E
) suggests that NO
3 is electrostaticaly adsorbed onto HS
in a process similar to pyrophosphate retention [42]. The
decrease of the peak of 1348 cm1 as metal concentration
rises, giving rise to 1423 cm1 (B2 ) and 1355 cm1 (A1 ),
suggests the formation of [CuNO3 ]+ retained onto HS. This
complex had been described in water/acetone mixtures by
Castro and Jagodzinski [41,43].

5. Conclusions
The HS surface is heterogeneous, with highly narrow
microporosity. The shape of the isotherms at constant pH
changed with pH from L-type (pH 26) to S-type (pH 8) due
to the rise in the DOM percentage, which forms very stable
complexes with copper. The isotherm data do fit adequately
to a several-single-adsorption-processes-based model. When
pH is 2 the retention of Cu(II), as [Cu(H2 O)6 ]2+ , is the preferred retention mechanism. The retained quantity of Cu(II)
as [Cu(OH)(H2O)6 ]+ increases with pH. Starting from pH 4
the Cu(II) begins its precipitation and is the preferred retention mechanism at pH 8.02. Starting from pH 6, the Cu(II)
forms very stable complexes with DOM. The presence of
HS has a great influence on the precipitation process of
Cu(II), giving rise to amorphous precipitates instead of crystal phases. Metals distribute heterogeneously on HS surface
and accumulate on the humic phases not associated with
clays. When Cl ions are present, part of the Cu(II) form
[CuCl4 ]2 , which due to its negative charge is stable in solution; when the anion present is NO
3 the complex formed,
[CuNO3 ]+ , is retained onto the HS.

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