Anal. Chem.

2003, 75, 3168-3174

Kinetic Investigation of Eu(III)-Humate

Interactions by Ion Exchange Resins
1 ssler,* Gunnar Buckau, Thomas Rabung, and Jae-Il Kim
Jean-Marc Monsallier, Wolfram Schu

Forschungszentrum Karlsruhe, Institut für Nukleare Entsorgung, P.O. Box 3640, 76021 Karlsruhe, Germany

Dominic Jones, Rose Keepax, and Nick Bryan

Center for Radiochemistry Research, Department of Chemistry, University of Manchester, Oxford Road,
Manchester, United Kingdom, M13 9PL

The kinetic stability of radionuclides bound to aqueous 6.73,18 log K(EuHA) ) 6.4 19) and the property of excluding large
colloids is a determining factor in their migration from a colloidal particles due to the size of its beads. (The interaction of
radioactive waste repository. The cation exchangers Chelex- Eu(III) with Chelex resin can be treated as complexation with
100, Dowex 50Wx4, and Cellphos (cellulose phosphate) IDA according to ref 15.)
have been shown a promising tool for kinetic investiga- The external surface area of the resin beads contributes little
tions. This study assesses the applicability of different to the total surface area. The resins are suitable for the rapid
exchange resins for Eu humate dissociation kinetics separation of small metal species from colloidally associated metal
investigations. All resins were found to produce satisfac- species.
tory results. A systematic study of parameters affecting In the batch experiments, humic colloids and the ion exchange
the dissociation rates of Eu(III) humate complexes was resin compete for the added metal ions:
performed. A set of purified humic substances was found
B
k1
to behave in the same way. However, unpurified Aldrich Mez+ + HA {\ } MeHA (1)
A
k
humic acid showed significant differences. 1

B
k2
Humic materials can play an important role in the assessment Mez+ + Exchanger {\
A
k
} MeExchanger (2)
2

of radionuclide migration from a radioactive waste repository.1,2

They have a high complexation affinity toward metal cations,
especially those with higher oxidation state (Z g +2). Due to these
high complexation affinities and their large hydrodynamic size,
they are present in natural waters as organic colloids loaded with
metal cations.3 Investigations on the relevance of humic colloids
on the migration of radionuclides have shown the importance of
kinetics. Indeed, the kinetic stability of radionuclides bound to
aquatic colloids determines their colloid-borne migration.
Different methods4-12 are used to investigate the dissociation
kinetics of metal humate complexes. The ion exchange batch
technique has already been used successfully6,5,13-17 and seems
to be a promising tool for kinetics investigations. Exchange resins
can be very useful for chemical speciation and determination of
metal humate complexation since they have comparable reactivity
to humic materials for trivalent f-elements (log K(Eu(IDA)+) )
* Corresponding author. Phone: +49 7247 82 6024. Fax: +49 7247 82 3927.
E-mail: wolfram@ine.fzk.de.
(1) Choppin, G. R. Radiochim. Acta 1988, 44/45, 23-28.
(2) Kim, J. I. In Handbook on the Physics and Chemistry of the Actinides; Freeman,
A. J., Keller, C., Eds.; Elsevier Science Publication: New York, 1986; Chapter
8.
(3) Kim, J. I.; Delakowitz, B.; Zeh, P.; Lin, X.; Ehrlicher, U.; Schauer, C.; Probst,
T. Migration behavior of radionuclides. In Colloid migration in groundwa-
ters: Geochemical interactions of radionuclides with natural colloids. Final
report; European Commission, 1996.
(4) Choppin, G. R.; Nash, K. L. J. Inorg. Nucl. Chem. 1981, 43, 357-359.
(5) Cacheris, W. P.; Choppin, G. R. Radiochim. Acta 1987, 42, 185-190.
In typical ion exchange batch experiments, the exchanger and
the humic colloid concentrations exceed the metal ion concentra-
(6) Colston, B. J.; van Elteren, J. T.; Kolar, Z. I.; de Goeij, J. J. M. Radiochim.
Acta 1997, 78, 111-115.
(7) Artinger, R.; Kienzler, B.; Schuessler, W.; Kim, J. I. J. Contam. Hydrol. 1998,
35, 261-275.
(8) Geckeis, H.; Rabung, T.; Kim, J. I. In Effects of humic substances on the
migration of radionuclides: complexation and transport of actinides; Buckau,
G., Ed.; Second technical progress report. FZKA 6324; Karlsruhe, 1999; Vol.
FZKA 6324, pp 47-58.
(9) Figura, P.; McDuffie, B. Anal. Chem. 1980, 52, 1433-1439.
(10) Burba, P. Fresenius J. Anal. Chem. 1994, 348, 301-311.
(11) Langford, C. H.; Khan, T. R. Can. J. Chem. 1975, 53, 2979-2984.
(12) Clark, S. B.; Choppin, G. R. In Chemical Modeling of Aqueous Systems II;
Melchior, D. C., Bassett, R. L., Eds.; ACS Symposium Series 416; American
Chemical Society: Washington, DC, 1990; Vol. 416, pp 519-525.
(13) Burba, P.; Rocha, J.; Klockow, D. Fresenius J. Anal. Chem. 1994, 349, 800-
807.
(14) King, S. J.; Warwick, P.; Hall, A.; Bryan, N. D. Phys. Chem. Chem. Phys.
2001, 3, 2080-2085.
(15) Geckeis, H.; Rabung, T.; Ngo Manh, T.; Kim, J. I.; Beck, H. P. Environ. Sci.
Technol. 2002, 36, 2946-2952.
(16) Langford, C. H.; Cook, R. L. Analyst 1995, 120, 591-596.
(17) Chakrabarti, C. L.; Lu, Y.; Cheng, J.; Back, M. H.; Schroeder, W. Anal. Chim.
Acta 1993, 276, 47-64.
(18) Martell, A. E.; Smith, R. M. NIST Critically Selected Stability Constants of
Metal Complexes Database, Version 2.0; U.S. Department of Commerce,
1995.
(19) Czerwinski, K. R.; Kim, J. I.; Rhee, D. S.; Buckau, G. Radiochim. Acta 1996,
72, 179-187.

3168 Analytical Chemistry, Vol. 75, No. 13, July 1, 2003 10.1021/ac020668r CCC: $25.00 © 2003 American Chemical Society
Published on Web 05/14/2003
tion. Equations 1 and 2 then become pseudo-first-order reactions. atmosphere, are 2.90 ( 0.30 (WBPHA2) and 4.08 ( 0.30 mequiv
The reaction rates are defined as g-1 (WBFA2).22
Commercially available humic acid (sodium salt, C 41.48%, O
B1 ) [HA]k
R B1 (3) 46.05%, H 3.51%, N 0.42%, and Na 8.54%) from the Aldrich Chemical
Co. was used in the experiments (no purification). Its PEC
B2 ) [Exchanger]k
R B2 (4)
determined by pH titration under an Ar atmosphere is 5.39 ( 0.20
mequiv g-1.23 All chemicals were of analytical grade. Stock
solutions of Aldrich humic acid and WBFA2 fulvic acid were
To enable the direct determination of the metal humic dissociation
prepared by dissolution of the relevant humic sample (1.00 ( 0.05
rate constant, rather than to use a multiparameter fit, the
g) in deionized water (100.0 cm3). WBPHA2 stock solutions were
association rate of metal ions in solution with the ion exchange
prepared by dissolving the humic (1.00 ( 0.05 g) in NaOH solution
B2) has to be at least 1 or 2 orders of magnitude faster
resin (R
(0.1 M, 20.0 cm3) followed by neutralization to pH 6 (HNO3) and
than the association rate of metal ions with humic colloids (R B1).
dilution to 100 mL with deionized water. Humic equivalent
However, eqs 1 and 2 only describe the principal competing
concentrations were calculated using the same method as for
reaction. Kinetic models to describe the system of metal/humic/
humic GoHy-573 above.
exchange resin are more complicated and consider parallel, e.g.,
Dowex 50Wx4, 100-200 mesh, was obtained from Lancaster
refs 4 and 16 and serial reactions, e.g., ref 20.
Synthesis. The exchange capacity of this cation exchanger is 4.8
Further investigation of the ion exchange batch technique is
mequiv (g of dry weight)-1.
necessary to understand the influence of exchange resins on metal
Procedure Used at INE. The Chelex resin was purified with
humate complexes. The intention of this study is to determine
0.1 HNO3 overnight and equilibrated with MES buffer at the pH
the influence of ion exchangers on the dissociation behavior of
of the samples. Then, it was washed with distilled water at neutral
Eu humate complexes. A systematic study of the parameters
pH. For the experiments, the Chelex resin (50-100 mesh, 10.0
influencing the kinetics of dissociation of metal humate complexes
g) was adjusted to pH 6 and I ) 1 equiv dm-3 by washing with 7
is performed.
L of a sodium acetate and acetic acid buffer solution. The buffer
solution was prepared by mixing equal volumes of sodium acetate
EXPERIMENTAL SECTION
(I ) 0.1 equiv dm-3) and sodium nitrate (I ) 0.9 equiv dm-3) and
The experiments were performed in two different laboratories
adjusting to pH 6 ( 0.1 (using HNO3 and NaOH). Since the
(FZK-INE and U-MAN) using different techniques and different
experiments were performed at pH 6.0 (or less), the effect of
reagents.
hydrolysis and carbonate complexation could be neglected.
Reagents Used at INE. The humic acid investigated is GoHy-
All experiments were conducted in aerobic conditions using
573, isolated from one of the deep groundwaters (depth, 139 m) 152Eu (lifetime, 13.33 years). The solutions are stored in 40-cm3
of the Gorleben site located in Northern Germany. The purification
vials under ambient air temperature (22 ( 2 °C) and shaken from
process and the characterization of GoHy-573 can be found
time to time. For each sampling date, a separate set of three vials
elsewhere.21 Its proton exchange capacity (PEC) determined by
was prepared. In all cases, unless indicated, the humic acid
pH titration under an Ar atmosphere is 5.38 ( 0.20 mequiv g-1.21
solution was prepared to the pH and ionic strength of interest
Stock solutions are prepared by dissolution of a known amount
and equilibrated 24 h before adding europium cation. After metal
of humic acid in 0.1 M NaOH rapidly followed by dilution with
cation addition, the pH was checked again and readjusted to the
0.1 NaClO4 containing 10-2 M MES buffer (2-mospholineethane-
desired value. The Chelex resin (0.1-4 mg) was added to the
sulfonic acid). The pH is adjusted to 6.0 (or 3.0) by addition of
metal/humic solutions after 1 or 456 h, respectively. After different
HClO4. The humic acid concentration is expressed in molar units
time periods, the resin is sedimented by centrifugation and an
by multiplying a given weight concentration (g dm-3) by the PEC
aliquot of the supernatant containing the humic materials was
(mequiv dm-3) divided by the charge of the metal ions under
sampled out and measured by γ-counting (Canberra, HPGe
investigation (z). Thus, for Eu(III), the humic acid concentration
detector, model GC 7021, relative efficiency 60%). The amount of
is expressed as [HA(III)].
Eu bound by Chelex could be obtained by the difference from
Chelex-100 resin is obtained from Bio-Rad (100-200 mesh).
the total initial europium concentration.
The exchange capacity of this cation exchanger is 2.0 mequiv (g
A set of experiments was performed to identify the behavior
of dry weight)-1. MES buffer and NaClO4 were obtained from
of the Chelex resin on the Eu humate complex. In a second stage,
Aldrich Chemical Co. (analytical grade reagents).
the influence of Chelex concentration (3, 10, 30, and 100 g dm-3)
Reagents Used at U-MAN. The humics WBPHA2 (peat
on the Eu dissociation from humic colloids was investigated. This
humic acid) and WBFA2 (aquatic fulvic acid) were isolated from
kinetics investigation was performed for different humic acid
soil and surface water samples respectively, which were taken
concentrations (3, 10, 30, and 100 mg dm-3) and two metal humic
from Whitray Fell, North Yorkshire, U.K. The details of their
colloids conditioning time (tc ) 1 and 456 h).
isolation and purification can be found elsewhere.22 Their proton
Procedure Used at U-MAN. The resin (Dowex 50Wx4 100-
exchange capacities, determined by pH titration under a N2
200mesh) was completely converted to the sodium form by
(20) Schüssler, W.; Artinger, R.; Kienzler, B.; Kim, J. I. Environ. Sci. Technol. washing successively with HCl (2.0 mol dm-3, 500 cm3), distilled
2000, 34, 2608-2611. H2O (500 cm3), NaCl (3.0 mol dm-3, 500 cm3), distilled H2O (500
(21) Kim, J. I.; Buckau, G.; Li, G. H.; Duschner, H.; Psarros, N. Fresenius J. Anal.
Chem. 1990, 338, 245-252. cm3), NaOH (0.1 mol dm-3, cm3), and distilled H2O (500 cm3).
(22) Bryan, N. D.; Robinson, V. J.; Lives, F. R.; Hesketh, N.; Jones, M. N.; Lead,
J. R. Geochim. Cosmochim. Acta 1997, 61, 805-820. (23) Kim, J. I.; Rhee, D. S.; Buckau, G. Radiochim. Acta 1991, 52/53, 49-55.

Analytical Chemistry, Vol. 75, No. 13, July 1, 2003 3169

The resin (Dowex 50Wx4 100-200 mesh and cellulose phosphate
sodium salt) was then stirred with the appropriate NaClO4 solution
(I ) 0.01, 0.1, and 1 equiv dm-3) for 4-6 h at pH 6 ( 0.1, before
air-drying.
In the batch procedure, Eu(III) solutions (10-6-10-7 mol dm-3)
containing radioactive tracer quantities of 152Eu (1.0 kBq) were
equilibrated with Aldrich humic acid (10 and 100 mg dm-3) at
pH 6 ( 0.1. The ionic strength of each solution (I ) 0.01, 0.1, and
1 equiv dm-3) was adjusted using NaClO4. After an equilibration
period (1, 3, 7, 8, 14, 21, and 80 days), aliquots of each solution
(8.0 cm3) were added to dry, conditioned resin (Dowex 50Wx4
100-200 mesh, 1.5 g, for I ) 0.01 and 0.1 equiv dm-3 systems,
cellulose phosphate sodium salt, 1.0 g, and Chelex, 1.5 g for the
I ) 1 equiv dm-3 systems) in sterile polysulfone tubes. For each
system, three replicates were laid on their side and left to shake
in a thermostated water bath (25 and 60 °C). At regular intervals,
the tubes were stood upright for 5 min and the resin was allowed
to settle. A 1.5-cm3 aliquot of the solution was then removed and
analyzed using γ-spectrometry (Canberra, HPGe detector, model
GC 3819, rel. efficiency 50%) to measure the concentration of
solution-phase 152Eu. After analysis, the aliquot was returned to
the experiment.
RESULTS AND DISCUSSION
First the ion exchanger/humic colloids/europium systems are
investigated with regard to processes that may bias the results of
Eu humic colloid dissociation experiments. Then parameters that
may influence the humic colloid Eu interaction kinetics are
systematically investigated.
Processes That May Bias Eu Humic Colloid Dissociation
Experiments. No influence of Chelex addition on [Na] in the
presence or absence of buffer could be observed. The stirring
and shaking rates were chosen to ensure that the measured effects
were not influenced by Eu diffusion to the exchange resin.
The possible sorption of humic colloids onto Chelex was
studied at pH 6.0 and I ) 0.01 equiv dm-3. Humic and Chelex
concentrations were varied over the range of experimental
conditions ([HA] ) 3-100 mg dm-3, [Chelex] ) 3-100 g dm-3).
The UV-visible spectrum of humic acid was measured, between
350 and 650 nm, before and after contact (1-2 days) with the
Chelex.
In the pH 6 experiments, there was no appreciable change in
the UV spectrum for Chelex concentrations from 3 to 30 g dm-3.
However, for the highest Chelex concentration (100 g dm-3) and
the two lower humic colloid concentrations (3 and 10 mg dm-3),
10-20% of the humic colloids were attached to the Chelex within
2 days.
As a consequence, the sorption of humic colloids onto the
Chelex can be neglected for most experimental conditions at pH
6. Only for the highest Chelex concentration and humic colloid
concentrations up to 10 mg dm-3 do sorption effects have to be
considered. However, even under these conditions, the sorption
of humic colloids onto the Chelex resin is a second-order effect.
Similar results were reported by refs 1 and 15.
The same technique was used to investigate possible interac-
tion of humic with Dowex (188 g dm-3) and Cellphos (62.5 g
dm-3). The experimental conditions were the same as for the
Chelex investigations, except the ionic strength that was varied
3170 Analytical Chemistry, Vol. 75, No. 13, July 1, 2003
Figure 1. Influence of humic type on Eu dissociation from humic:
[Chelex] ) 100 g dm-3, tc ) 120 h, [Dowex] ) 188 g dm-3, tc ) 168
h, [Cellphos] ) 188 g dm-3, tc ) 168 h, [Eu] ) 10-7 mol dm-3, [HA]
) 10 mg dm-3, pH 6, I ) 0.01 equiv dm-3, and T ) 25 °C.
from 0.01 to 1 equiv dm-3. No interaction of humic material
with the resins was found, also confirmed by the findings of refs
2 and 24.
Additional experiments at pH 4 (I ) 0.01 equiv dm-3 for [HA]
) 10 mg dm-3 and [Chelex] ) 100 g dm-3) showed that up to
75% of the humic colloids were attached to the Chelex resin.
Therefore, for low pH values, sorption effects have to be
considered when interpreting the experimental findings.
Influence of System Parameters on Dissociation Kinetics.
Humic Substance Origin. Figure 1 shows results from both
laboratories. The FZK-INE data are concentrated at shorter time
periods and the U-MAN data at longer. This is the case throughout
this study due to the different techniques used. Figure 1 shows
that the purified humic acids GoHy-573, WBPHA2, and WBFA2
behave in a very similar way. All these samples were purified using
the standard purification procedure described by ref 25. However,
the commercial available unpurified Aldrich humic shows distinct
behavior. This indicates that the purification technique may have
an impact upon dissociation kinetics, whereas in equilibrium
adsorption experiments humic purification and origin were shown
to have no effect within the experimental uncertainties.3,23 Most
of the data shown in Figure 1 were measured at I ) 0.01 equiv
dm-3. Changing I to 1 equiv dm-3 for the Aldrich humic produces
behavior similar to the purified samples.
Type of Exchange Resin. The plots in Figure 1 were obtained
using all three resins (Chelex, Dowex, Cellphos). All three resins
show the same general behavior. This suggests that the resin type
has no significant effect on the results. However, this finding has
to be checked, because different humics were used in the
experiments with different resins.
Concentration of Exchange Resin. This investigation was
performed for four Chelex concentrations (3, 10, 30, and 100 g
dm-3) at four different humic substances concentrations (3, 10,
30, and 100 mg dm-3) and for two conditioning times (1 and 456
(24) Rao, L.; Choppin, G. R.; Clark, S. B. Radiochim. Acta 1994, 66/67, 141-
147.
(25) Kim, J. I.; Rhee, D. S.; Buckau, G.; Morgenstern, A. Radiochim. Acta 1997,
72, 179-187.
Figure 2. Influence of Chelex concentration on Eu dissociation from
GoHy-573 humic acid: [HA] ) 100 mg dm-3, [Eu] ) 10-6 mol dm-3,
pH 6, I ) 0.01 equiv dm-3, tc ) 1 h, and T ) 25 °C.
h). To have a constant metal/binding sites ratio, the Eu concen-
tration was varied in the same extent as the humic concentration
(3 × 10-8, 10-7, 3 × 10-7, and 10-6 mol dm-3). All the experiments
were performed at pH 6.0 and I ) 0.01 equiv dm-3 (NaClO4).
Figure 2 shows that the Chelex concentration has an influence
on the Eu humic colloid dissociation rate. An increase of the
Chelex concentration enhances the dissociation rate. It can be
ruled out that these findings are biased by humic sorption onto
Chelex, as shown above.
Similar results were found for the HYPHAN exchange resin
by ref 10 for Cu(II) and for Dowex 50Wx4 by ref 14 for Eu(III).
The experiments by ref 14 indicate that the higher the exchanger
concentrations and reaction times the smaller the influence of
exchanger concentration becomes, which is in accordance with
our results (Figure 2).
Humic/Metal Mole Ratio. Several investigations on the effect
of the humic/metal mole ratio (metal loading) on the dissociation
behavior of Ni, Cu, Pb, and Al have been published.13,26-29 Most
of these studies focus on humic/metal mole ratio, neglecting
effects of absolute concentrations of humics and metal. Conse-
quently, variations of humic or metal concentration are treated in
the same manner. However, the relative amount of sites on the
ion exchanger and on the humic determines the rate-limiting
reaction whatever metal concentration is used. Therefore, in this
paper, the effects of humic and metal concentration are discussed
separately.
Concentration of Humic. The experiments showed that the
humic concentration affects the Eu removal from solution (Figure
3). An increase in the humic concentration slows down the Eu
uptake by the exchange resin. This effect was also found for Ni,26,27
Cu,28,29 Pb, and Al.29
(26) Sekaly, A. L. R.; Chakrabarti, C. L.; Gregoire, D. C. In EnviroAnalysis,
Biennial International Conference on Chemical Measurement and Monitoring
of the Environment; Clement, R., Burk, B., Eds.; Conference Secretariat,
Chemistry Dept., Carleton University: Ottawa, ON, Canada, 1998; pp 611-
618.
(27) Lavigne, J. A.; Langford, C. H.; Mak, M. K. S. Anal. Chem. 1987, 59, 2616-
2620.
(28) Rate, A. W.; McLaren, R. G.; Swift, R. S. Environ. Sci. Technol. 1993, 27,
1408-1414.
(29) Lu, Y.; Chakrabarti, C. L.; Back, M. H.; Grégoire, D. C.; Schroeder, W. H.
Int. J. Environ. Anal. Chem. 1995, 60, 313-337.
Figure 3. Influence of humic acid concentration on Eu dissociation
from Aldrich and GoHy-573 humic acid. To have a constant metal/
binding sites ratio in the GoHy experiments, the Eu concentration
was varied to the same extent as the humic concentration (3 × 10-8,
10-7, 3 × 10-7, and 10-6 mol dm-3): [Chelex] ) 100 g dm-3 and tc
) 120 h. In the Aldrich experiments, a Eu concentration of 10-7 mol
dm-3 was used: [Dowex] ) 188 g dm-3 and tc ) 168 h. For all
experiments, pH 6, I ) 0.01 equiv dm-3, and T ) 25 °C.
This behavior can be explained as follows. The measured Eu
removal from the humic colloids is the net effect of two reaction
rates (R B1,R
B2, eqs 3 and 4). Each rate is the product of a rate
constant and the competing ligand concentration. Typical values
B1 ) (0.2-8) × 10-3
for reaction rates for Eu(III) and Am(III) are R
s (for [HA] ) 3-100 mg dm , B
-1 -3 k1) 31 s equiv dm-3 20) and
-1
B2 ) (0.1-3) × 10 s (for [Chelex] ) 3-100 g dm-3, B
R -1 -1 k2) 1.7
s-1 equiv dm-3 calculated from Eu data from ref 15). In case of
high exchange resin concentration in the Eu experiments R B2 is
more than 1 order of magnitude higher than R B1 and the rate-
limiting step is the dissociation of Eu from its humic colloid
complex. In case of low-exchange resin concentration ([Chelex]
) 3 g dm-3) and high humic colloid concentration ([HA] ) 100
mg dm-3) R B1 equals RB2 and both rates control the measured Eu
concentration in solution. As the reassociation of Eu with the
humic colloids becomes significant, the Eu uptake by the
exchange resin is slowed down. For these experimental condi-
tions, the Eu humic colloid dissociation rate is not equal to the
measured Eu removal from solution. Additional information is
required to calculate or fit the Eu humic colloid dissociation rate
from such experiments.
Initial Europium Concentration. The influence of europium
concentration was investigated for two concentrations ([Eu] )
10-7 mol dm-3 and [Eu] ) 10-5 mol dm-3) and two contact times
(1 and 120 h) for the GoHy-573 (Figure 1, Supporting Information).
For the chosen Eu concentrations, an influence of [Eu]0 on the
Eu humate dissociation rate for the two conditioning times
investigated was found. This effect may be attributed to different
Eu humic acid loadings (Table 1), resulting in slightly different
Eu humic acid dissociation kinetics. For Ni, the same general
trend was found by refs 13 and 26.
Analytical Chemistry, Vol. 75, No. 13, July 1, 2003 3171
Table 1. Eu Humic Acid Equilibrium Speciation at pH 6,
I ) 0.1 mequiv dm-3a
[Eu]tot, [HA]tot, [MeHA]/ [Me]free/ [HA]free/
mol dm-3 mg dm-3 [Me]tot, % [Me]tot % [HA]tot, %
10-7 10 96.7 3.3 99.2
10-6 10 96.4 3.6 91.8
10-5 10 88.1 11.9 25.1
a PEC ) 5.4 mequiv g-1 mean of GoHy-573 and Aldrich HA,23 LC
) 0.65 and log K ) 6.418) in GoHy-573 and Aldrich solutions containing
10 mg dm-3 for different Eu concentrations.
Figure 4. Influence of pH on Eu dissociation from GoHy-573 humic
acid. Solid symbols: pH remains constant (pH ) 3 or 6) throughout
the whole experiment. Open symbol: The pH of the humic solution
was initially 6.0 when Eu was added. After 2 min, the solution pH
was brought down to 3.0 by addition of small aliquots of 0.1 M HClO4.
Then, the metal-humic acid contact time was 1 h before addition of
Chelex: [HA] ) 10 mg dm-3, [Chelex] ) 10 g dm-3, [Eu] ) 10-7 mol
dm-3, I ) 0.01 equiv dm-3, tc ) 1 h, and T ) 25 °C.
The behavior of the Aldrich humic acid was also studied ([Eu]
) 10-6 mol dm-3 and [Eu] ) 10-7 mol dm-3, tc ) 168 h). The
Aldrich humic shows the same general behavior. The only
difference is that the Aldrich plots converge at long times. This
suggests that for the Aldrich humic the desorption mechanisms
for the longest living fraction are the same at these two metal
concentrations. This could not be observed for the GoHy-573 due
to the short reaction period in the experiments. In Figure 1 in
the Supporting Information, the Aldrich and GoHy plots are in
the same region. This is due to the different amount of exchange
resin used in the experiments.
Solution pH. The influence of solution pH was investigated
for pH 6.0 and pH 3.0. The solution conditions were identical for
all the samples: [HA] ) 10 mg dm-3, [Eu] ) 10-7 mol dm-3, I )
0.01 equiv dm-3 fixed with NaClO4 and addition of 10 g dm-3
Chelex. The pH of the humic solution was already fixed at 3.0,
respectively, at 6, when Eu was added. There was no major change
of pH upon Eu addition. The contact time before addition of
Chelex was varied from 1 to 120 h. In Figure 4 the results for 1-h
contact time are shown. Increasing the pH from 3 to 6 results in
a faster dissociation of the Eu from the humic acid. This may be
attributed to different humic colloid structures for the different
pH values that may influence the dissociation behavior of Eu.
Qualitatively the same result was found for 120-h contact time;
however, the effect of pH was less pronounced. These findings
3172 Analytical Chemistry, Vol. 75, No. 13, July 1, 2003
are in accordance with other authors investigating Fe(II),30
Cu(II),28 Ni(II),27 U(VI), and Eu(III).24 They suggest that due to
a more open structure of the humic colloids at higher pH the
dissociation rates should increase with increasing pH.
At pH 3, considerable sorption of humic colloids onto the
Chelex resin takes place. However, sorption of Eu bearing humic
colloids would result in a faster Eu removal from solution at lower
pH. The opposite is found in the experiments. Therefore, the
experimental result cannot be attributed to this sorption process.
Initial pH. The intention of this experiment was to determine
whether the initial pH of the humic solution has an influence on
the dissociation rate of the metal humate complex, taking into
account that the final pH is identical. The pH of the humic solution
was initially 6.0 when Eu was added. After 2 min, the solution pH
was brought down to 3.0 by addition of small aliquots of 0.1 M
HClO4. Then, the metal-humic acid contact time was 1 h before
addition of Chelex. Figure 4 shows that in this experiment the
Eu dissociation behavior is similar to the dissociation observed
at pH 6. This demonstrates that the initial pH in which the metal
cation sees the humic colloids upon its addition has a drastic
influence on the dissociation rates. Despite the fact that the final
solution pH is the same in both experiments, one observes
different dissociation kinetics. Throughout the course of the
dissociation experiment, one studies the dissociation kinetics
under unstable pH conditions from the viewpoint of humic acid
structure. There is rearrangement in the geometry of the humic
colloids. For longer contact time (120 h), the difference observed
is smaller. Indeed, during the longer conditioning time, humic
colloids have time to rearrange their structure to match the
structure corresponding to the final solution pH. In all other
experiments of this study, the pH of the humic solution was fixed
to the pH under investigation before metal cation addition.
Ionic Strength. The influence of the ionic strength was
investigated for three NaClO4 concentrations (I ) 0.01, 0.1, and
1 equiv dm-3). We observed that an increase in the ionic strength
increased the Eu humate dissociation rate for both Aldrich and
GoHy humic acid (Figure 2, Supporting Information). This may
be attributed to a more open colloid structure at the lower ionic
strength.28,31 Despite this difference, all of the plots show the same
general slope.
Ionic Strength of Desorption. In two experiments, the ionic
strength during the contact time of the Eu with the groundwater
prior to addition of the exchange resin was different from the ionic
strength during desorption. In both cases, desorption was carried
out at I ) 1 eq dm-3, but the contact time ionic strengths were I
) 0.1 equiv dm-3 and I ) 0.01 equiv dm-3, respectively. The data
for the I ) 0.01 equiv dm-3 contact time are plotted in Figure 2
of the Supporting Information. The results show that the behavior
in this system is most similar to the system contacted and
desorbed at I ) 1 equiv dm-3. This behavior is in contrast to that
observed with pH, where the pH of contact time had a definite
effect provided that the time allowed for the system to adapt to
the new pH was short (1 h). In the case of ionic strength
experiments, the time allowed for the system to adapt to the new
ionic strength was in the order of minutes. Therefore, for ionic
strength, only the conditions of desorption seem to be important.
(30) Rey, F.; Calle, E.; Casado, J. Int. J. Chem. Kinet. 1998, 30, 63-67.
(31) Swift, R. S. Soil Sci. 1999, 164, 790-802.
Figure 5. Influence of contact time: [Chelex] ) 100 g dm-3, Figure 6. Calculation of Eu bound to GoHy-573 humic acid using
[Dowex] ) 188 g dm-3, [HA] ) 10 mg dm-3, [Eu] ) 10-7 mol dm-3, KICAM. Parameters are taken from ref 20. Symbols: Eu/GoHy 573-
pH 6, and T ) 25 °C. (purified)/Chelex experiment, experimental conditions: [HA] ) 100 mg
dm-3, [Chelex] ) 30 g dm-3, [Eu] ) 10-6 mol dm-3, and pH ) 6.
Shaded area: calculation of Am dissociation behavior using the rate
In all other experiments of this study, the ionic strength of constants determined in ref 20 (Table 2, Supporting Information),
the humic solution was fixed to the ionic strength under investiga- experimental conditions: GoHy 2227, [HA] ) 80 mg dm-3, [Am] ) 2
× 10-6 mol dm-3, and pH 7.5.
tion before metal cation addition.
Temperature. The effect of temperature on desorption was
investigated for T ) 25 and 60 °C (Figure 3, Supporting
constants. Therefore, we decided to present all the experimental
Information). At 60 °C, at any time of the experiment and for any
results with qualitative interpretations but without any data-fitting
contact time, there is less Eu bound to Aldrich humic acid than
exercise. The development of an appropriate kinetic model is in
at 25 °C. However, for the longest living fraction, analysis of the
progress. However, the consistency of the presented data, assum-
data shows that the first-order rate constants for desorption show
ing Eu(III) to be a chemical homologue for Am(III), with former
no significant difference between the two temperatures. This
investigations on humic colloid americium interaction has to be
shows that the activation barrier responsible for slow desorption
shown.
must be largely entropic in nature. This is consistent with
For the experimental conditions in Am column experiments
structural rearrangement being the rate-determining step as
in near natural systems,7 the dissociation of the Am from the
suggested by ref 32.
humic colloid was identified to be the rate-limiting reaction. These
The data for 25 °C show for short reaction times an effect of
experiments were described by a kinetic reaction scheme (Table
contact time. With increasing reaction time, this effect decreases.
1, Supporting Information20). Assuming Eu is a homologue to Am,
However, no influence of contact time is found for the experiment
the rate constants determined for Am (Table 2, Supporting
at elevated temperature.
Information20) can be used to model the Eu dissociation from the
Contact Time. Figure 5 shows the effect of contact time (tc )
humic colloids. As shown before, variation of system parameters
1-1920 h) on desorption. The data in the figure show the same
influences the metal humic dissociation behavior. Therefore, the
general behavior. For longer contact times, more Eu is bound to
Am rate constants should be only used to describe Eu dissociation
humic acid for all reaction times and for all humics (T ) 25 °C).
behavior in comparable systems. In Figure 6, the model calcula-
However, again the Aldrich humic acid plots in a region different
tions using the Am reaction rates are compared to Eu dissociation
from the Gohy-573. Also, the Aldrich data converge at long
experiments. The system parameters used in the Am and Eu
reaction times, whereas the GoHy data do not. These findings
experiments were comparable, despite solution pH (pH(Am) )
are consistent with a buildup of less exchangeable Eu with contact
7.5, pH(Eu) ) 6) and the solid phase used (Am, aeolian quartz
time. Similar behavior was found in previous studies on Cu(II)10
sand; Eu, Chelex). The amounts of surface sites in the Am and
and Eu(III).14,15,33
Eu experiments were comparable. From Figure 6, it is clear that
Reaction Rate Constants and Comparison with Am. The
the overall picture for Am experiments with near-natural samples
experimental data presented can be used to derive reaction rate
and Eu experiments with defined laboratory systems is the same.
constants. However, the determined rate constants depend on the
As in the Am experiments, the Am dissociation from the humic
kinetic model used for evaluation. At the moment, none of the
colloid was the rate-limiting step, and the same can be assumed
available models (e.g., refs 20 and 34-38) was able to describe
for Eu (for the system parameters of the chosen Eu experiment).
the whole set of experimental data with one consistent set of rate
Differences between the calculated Eu dissociation behavior and
(32) Engebretson, R. R.; Von Wandruszka, R. Environ. Sci. Technol. 1998, 32,
488-493. (36) Warwick, P. W.; Hall, A.; Pashley, V.; Bryan, N. D.; Griffin, D. J. Contam.
(33) Choppin, G. R.; Clark, S. B. Mar. Chem. 1991, 36, 27-38. Hydrol. 2000, 42, 19-34.
(34) Clark, S. B.; Choppin, G. R. ACS Symp. Ser. 1996, No. 651, 207-219. (37) Langford, C. H.; Gutzman, D. W. Anal. Chim. Acta 1992, 256, 183-201.
(35) Artinger, R.; Schuessler, W.; Schäfer, T.; Kim, J. I. Environ. Sci. Technol. (38) El Mrabet, R.; Abril, J. M.; Manjón, G.; Garcı́a Tenorio, R. Water Res. 2001,
2002, 36, 4358-4363. 35, 4184-4190.

Analytical Chemistry, Vol. 75, No. 13, July 1, 2003 3173

the experimental results had to be expected, as different solid
phases were used and the solution pH varied by 1.5 units. The
effect of different solid phases becomes more pronounced for
longer reaction times as here the properties of the solid phase
becomes more and more important in the batch experiment.
Database. The above evaluation of data is based on 78
different data sets (32 from U-MAN and 46 from FZK-INE). Only
a part of the data could be presented within this paper. However,
to enable other research groups to work with these data or use
them for modeling purposes, the whole set of data will be given
in the Supporting Information.
CONCLUSION
This study shows that different ion exchange techniques
investigating kinetic metal ion humic interactions from different
laboratories have produced comparable results. However, to
enable the comparison of the results, all experimental details are
important and have to be published.
Purified humic substances (GoHy-573, WBPHA2, WBFA2)
show very similar desorption behavior. In contrast, unpurified
Aldrich humic acid shows significantly different behavior. Experi-
ments using different amounts of exchange resin revealed that
the more resin used, the less Eu is found in solution at any
reaction time. This only holds true up to a certain amount of resin
(∼0.2 equiv dm-3). From this point, desorption from the humic
becomes the rate-limiting step and using more resin shows no
effect.
With increasing humic acid concentration, contact time, or
both, the amount of Eu(III) remaining bound to the humic at any
given reaction time increases. For increasing pH ionic strength
and temperature, the amount of Eu(III) remaining bound to the
humic at any given reaction time decreases. For pH, provided
that the system only has a short time to adjust, the humic seems
3174 Analytical Chemistry, Vol. 75, No. 13, July 1, 2003
to remember the pH during contact time. However, for ionic
strength, the conditions during contact time seem to have no effect
regardless of the time for adjustment.
As the total initial Eu concentration increases, the absolute
amount of Eu sorbed to humics increases for all reaction times.
In contrast, the relative amount of metal bound is lower.
Up to now these findings could not be explained in detail. This
is due to an insufficient process understanding. Experiments to
improve this understanding are in progress.
However, the presented results reveal two very important
conclusions: (1) The overall picture in laboratory experiments
with near-natural and designed systems is the same; i.e., similar
reaction kinetics for Am and Eu humic colloids are observed. (2)
Ion exchange techniques are very well suited to investigate the
interaction kinetics of metals with humic colloids, and different
exchange resins reveal the same experimental results.
ACKNOWLEDGMENT
This paper has benefited from comments of two anonymous
reviewers, their help is gratefully acknowledged. The authors also
thank EPSRC and BNFL for funding.
SUPPORTING INFORMATION AVAILABLE
Database used to evaluate the above findings, consisting of
78 different data sets (32 from U-MAN and 46 from FZK-INE); in
addition, two more tables and three more figures are included.
This material is available free of charge via the Internet at http://
pubs.acs.org.
Received for review October 29, 2002. Accepted March 13,
2003.
AC020668R