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Research article
Department of Geology and Geological Engineering, Colorado School of Mines, Golden, CO 80401, United States
Hydrologic Science and Engineering Program, Department of Geology and Geological Engineering, Colorado School of Mines, Golden, CO 80401, United States
Geological Sciences, University of Colorado at Boulder, CO 80401, United States
Hydrologic Science and Engineering Program, Environmental Science and Engineering Division, Colorado School of Mines, Golden, CO 80401, United States
a r t i c l e
i n f o
Article history:
Received 5 December 2008
Received in revised form 25 February 2009
Accepted 16 April 2009
Available online 20 April 2009
Keywords:
Cyclodextrin
Solubility enhancement
Metals
Remediation
a b s t r a c t
Carboxymethyl--cyclodextrin (CMCD) has been suggested as a complexing agent for
remediation of sites co-contaminated with metals and organic pollutants. As part of an attempt
to construct a geochemical complexation model for metal-CMCD interactions, conditional
formation constants for the complexes between CMCD and 7 metal ions (Ba, Ca, Cd, Ni, Pb, Sr, and
Zn) are estimated from experimental data. Stable metal concentrations were reached after
approximately 1 day and estimated logarithmic conditional formation constants range from 3.2
to 5.1 with condence intervals within 0.08 log units. Experiments performed at 10 C and
25 C show that temperature affects the solubility of the metal salts but the strength of CMCDmetal complexes are not affected by this temperature variation. The conditional stability constants
and complexation model presented in this work can be used to screen CMCD as a potential
remediation agent for clean-up of contaminated soil and groundwater.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Organic and inorganic contaminant mixtures present at
contaminated sites is one of the major challenges in
remediating soil and ground. Due to the fundamentally
different physiochemical properties of these contaminants,
research has to a large extent focused on remediating organic
and inorganic contaminants separately rather than with a
single treatment. Two basic approaches to remediation are to
wash (ex-situ) or ush (in-situ) the contaminated soil with
water (pump and treat) or with an agent to increase solubility
(enhanced ushing). If the complexing agent, or mixture of
complexing agents, is chosen appropriately both organic and
inorganic contaminants can be removed simultaneously. For
instance, biosurfactants (Mulligan et al., 2001) and solutions
of strong acids mixed with isopropyl alcohol (Semer and
Reddy, 1996) have successfully been used in bench scale
experiments. In both studies heavy metals were removed in
Corresponding author. Tel.: +1 303 471 3482; fax: +1 303 471 3482.
E-mail address: Magnus.Skold@Arcadis-us.com (M.E. Skold).
0169-7722/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jconhyd.2009.04.006
109
purity. All other chemicals were + 98% pure unless otherwise noted. The background ionic strength was controlled
by KNO3 in the multi-day experiments, while NaNO3 was
used in the 2-h experiments. In all titrations, the solutions
were purged with nitrogen gas (ultra high purity) prior to
reaction and the pH was adjusted with sodium hydroxide
solution.
All metal salts (Ba, Ca, Cd, Ni, Pb, and Zn) were oxalates,
except for SrSO4. The purity of Cd oxalate was not reported. Zn
and Ni oxalates were formed via precipitation from solutions
of metal nitrates and oxalic acid as described in Donia (1997).
XRD analysis showed that crystalline Ni and Zn oxalates
formed (data not shown).
The acidbase behavior of CMCD was investigated by
potentiometric titrations in a CO2(g) free atmosphere. The
titrations were performed in a glass vessel. Temperature was
kept constant at 25 C and background ionic strength was
50 mM KNO3 while pH was increased by adding incremental
volumes of 0.1 M NaOH. The pH was measured with a
combination glass electrode. Before titrating cyclodextrin
with NaOH, the CMCD-Na salt was converted to its acidic form
by passing 50 ml of a 100 g/l CMCD solution twice through a
column containing an ion exchange resin. Ion-exchange resin
(Rexyn 101H) was purchased from Fisher Scientic. The
CMCD solution was bubbled with nitrogen gas for at least 1 h
at pH near 3.3 prior to each titration in order to remove any
carbon dioxide.
Batch experiments aimed at determining conditional
stability constants for complexation between CMCD and
metal ions were performed in sealed 15 ml centrifuge tubes
submerged in a water bath to control temperature at 10 0.5 or
25 0.5 C. Two separate sets of experiments were performed.
A preliminary investigation at 10 and 25 C lasting 2 h was
performed prior to a second set of experiment at 25 C lasting
7 days. A small amount (2050 mg) metal salt was added to
10 ml solutions containing up to 20 g/l CMCD in 50 mM
background ionic strength. In the preliminary experiments,
background ionic strength was varied from 0 for 20 g/l CMCD
solutions, to 50 mM at the lower CMCD concentrations. In
the longer time experiments, the CMCD concentration ranged
from 0 to 100 g/l and background ionic strength was held
constant at 50 mM KNO3. Hydrogen ion activity was adjusted to
pH 6.00 0.05 in all CMCD solutions before adding the metal
salts. The pH was not controlled during the experiment to avoid
interference with buffering compounds; the nal pH varied
from 5.3 to 7.3. Effects of pH variations on the metal speciation,
such as formation of metal carbonates and hydroxides
was taken into account by geochemical modeling as explained
below. The centrifuge tubes were slowly rotated top-overbottom throughout the experiment to ensure constant and
gentle mixing.
The solid metal salt was separated from the aqueous
solution by 0.45 m ltering and the pH was measured
immediately. The aqueous metal concentration was subsequently analyzed with inductively couple plasma-optical
emission spectrometry (ICP-OES).
110
CMCD
2+
2+
+ Me
= CMCDMe
CMCDH2 = CMCDH
CMCDH
+ C2 O4
= CMCD
COOH = COO
+H
+H
+H
1 + B a0;CMCD2
!
p
6
The conditional stability constant for metal-CMCD complexation is calculated according to:
fCMCDMeg
KCMCD Me =
CMCD2 Me2+
Table 1
Logarithmic constants for aqueous metal-oxalate complexes used in
modeling (Martell and Smith, 1977).
Ba
Ca
Cd
Ni
Pb
Sr
Zn
MeC2O4
Me(C2O4)22
Me(C2O4)43
MeHC2O+
4
Me(HC2O4)2
2.31
2.54
3.89
5.16
4.91
NA
4.87
NA
2.69
5.66
NA
6.76
NA
7.65
NA
NA
5.06
NA
NA
NA
NA
NA
1.84
NA
NA
NA
NA
1.72
NA
NA
NA
NA
NA
NA
3.12
Fig. 1. Base titrations at 0.518, 0.698, 0.977, 1.22, and 1.49 g/L of CMCD. Solid
lines represent single-site model and dotted lines represent two-site model.
111
CaC2O4
CdC2O4
NiC2O4
PbC2O4
SrSO4
ZnC2O4
10 C
25 C
25 C
10 C
25 C
25 C
10 C
25 C
25 C
25 C
25 C
10 C
25 C
25 C
10 C
25 C
25 C
10 C
25 C
25 C
10 C
25 C
25 C
2h
2h
7 days
2h
2h
7 days
2h
2h
4.5 h
19 h
7 days
2h
2h
7 days
2h
2h
7 days
2h
2h
7 days
2h
2h
7 days
6.71
6.55
6.59
8.76
8.49
8.03
7.99
7.80
7.80
7.80
7.80
NA
NA
9.73
10.79
10.46
10.46
6.81
6.69
6.69
NA
NA
8.86
logKsp b
6.79 d 3.60
3.60
3.58
8.63 e 3.64
3.67
3.56
f
7.85
5.14
4.78
4.95
4.40
4.04
g
9.4
NA
NA
3.48
9.32 h 5.21
5.27
5.18
6.46 i 3.49
3.53
3.55
j
8.86
NA
NA
3.64
3.543.66
3.583.64
3.553.60
3.583.70
3.593.75
3.473.64
4.765.52
4.495.07
4.755.16
4.304.50
3.914.18
NA
NA
3.443.51
5.135.30
5.215.34
5.145.23
3.293.69
3.283.78
3.473.63
NA
NA
3.613.67
112
113
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