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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.
48
R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755
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
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
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
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.
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)
49
+ 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)
50
R.A. Alvarez-Puebla et al. / Journal of Colloid and Interface Science 270 (2004) 4755
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)
Knsm C
,
1 + KC
(11)
(12)
ns = (k1 /k2 )C b = AC b .
(13)
(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.
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.)
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
52
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)
(17)
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
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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