Journal of Hazardous Materials 363 (2019) 394–400

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Mobility and retention of indium and gallium in saturated porous media T

Kerstin Ringering, Yasmine Kouhail, Yinon Yecheskel, Ishai Dror , Brian Berkowitz
⁎

Department of Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot, Israel

ARTICLE INFO ABSTRACT

Keywords: Transport of indium and gallium is reported in laboratory column experiments using quartz sand as a model
Technology-critical elements porous medium representative of a groundwater system. With increased use of indium and gallium in recent
Transport years, mainly in the semiconductor industry, concerns arise regarding their environmental effects. The transport
Complexation and retention behavior of these two metals were quantified via batch and column experiments, and numerical
Humic acid
modeling. The effect of natural organic matter on indium and gallium mobility was studied by addition of humic
Modeling
Groundwater
acid (HA). Measured breakthrough curves from column experiments demonstrated different binding capacities
Soil-water between indium and gallium, stronger for indium, with the presence of HA affecting retention dynamics. For
Environmental contamination indium, the binding capacity on quartz decreases significantly in the presence of HA, leading to enhanced
mobility. In contrast, gallium exhibits slightly higher retention and lower mobility in the presence of HA. In all
cases, the binding capacity of gallium to quartz is much weaker than that of indium. These results are consistent
with the assumption that indium and gallium form different types of complexes with organic ligands, with
gallium complexes appearing more stable than indium complexes. Quantitative modeling confirmed that metal
retention is controlled by complex stability.

1. Introduction Increased industrial use often leads to increased environmental

Indium and gallium are metals of low abundance in the Earth’s
crust, with typical concentrations of 0.11–0.25 mg/L indium and
15–19 mg/L gallium [1,2]. These two chemical elements were of only
minor technical relevance in the past. Anthropogenic release was
mainly via pollution-intensive processes such as mining and burning of
fossil energy carriers in which indium and gallium were present as trace
metals [3]. Correspondingly, there has been only moderate interest in
these elements from the environmental sciences community.
However, over the last two decades, both indium and gallium have
played a key role in the modern semiconductor industry. They are
central to integrated circuits and photoelectric devices in products of
mass production, such as smartphones, tablet computers, and digital
cameras [4,5]. The predominant Ga compounds in semiconductors are
GaAs and GaN [6,7] while the most common use (> 50%) of indium is
as indium tin oxide (ITO), a transparent, heat reflective and electrically
conductive coating used on screens in electrical equipment [7–9]. Both
elements are extremely useful in these applications due to their rela-
tively high electron mobility and charge transfer efficiency [10] thus
they are often near irreplaceable. Consequently, there has been a
sudden and dramatic increase in the demand for indium and gallium in
the last decade (Fig. S1).
concentrations [3] and development of new potential environmental
sources such as e-waste [11] and biosolids [12]. For example, Toku-
maru et al. [11] reported an extremely high degree of indium con-
tamination in e-waste recycling soil with an enrichment factor > 40
compared to control site soil. Similarly, Poledniok [13] reported sys-
tematic higher concentrations of Ga in soil from an industrial area in
Poland compared to agricultural soil from the same region. With re-
spect to groundwater, Chen [4] reported that wells in an industrial area
in Taiwan had a mean Ga concentration of 19.34 μg/L, compared to
0.05 and 0.02 μg/L in groundwater from two non-industrialized zones,
and concentrations of 9.25 μg/L vs. 0.04 and 0.01 μg/L, respectively,
for In. These findings raise serious concern, given that gallium and
especially indium have negative impacts on living organisms, like re-
duction in root length and weight for Arabidopsis thaliana and rice
[3,14–16]. In addition to natural ecosystems, toxicity to various or-
ganisms was reported [17–20] and human health might also be affected
if indium and/or gallium reach groundwater systems that provide
drinking water [14]. In a different context, gallium has been applied to
diagnose tumors in medical tests as gallium citrate complexes [21] and
can thus be released from hospital wastewater plants.
Currently, the environmental speciation and the ecotoxicity of in-
dium and gallium are not well constrained. However, these elements

⁎
Corresponding author at: Department of Earth and Planetary Sciences, Weizmann Institute of Science, 234 Herzl St. P.O. Box 26, Rehovot, 7610001, Israel.
E-mail address: ishai.dror@weizmann.ac.il (I. Dror).

https://doi.org/10.1016/j.jhazmat.2018.09.079
Received 31 May 2018; Received in revised form 27 September 2018; Accepted 28 September 2018
Available online 06 October 2018
0304-3894/ © 2018 Elsevier B.V. All rights reserved.
K. Ringering et al.
are widely accepted to be predominantly trivalent, and hydrolyze in
solution (to Ga/In(OH)2+, Ga/In(OH)2+, Ga/In(OH)3° and Ga/In
(OH)4−). Moreover, these elements complex to hard inorganic ligands
when available, and precipitate readily in pure water [1]; both ele-
ments also complex with organic molecules rich in hydroxyl and car-
boxy groups [15]. Analogy to other metals suggests that toxicity may be
exhibited when concentrations in the environment change abruptly [3].
The transport behavior of indium and gallium in groundwater sys-
tems remains poorly understood; to date it has in essence not been
reported in the literature. Moreover, although the sorption behavior of
indium and gallium has been studied, to some extent, for technical
sorbents utilized for recovery (e.g., from aluminum and zinc ores
[22–25]), research on their interaction with typical minerals of soil
systems is only in its infancy [10,26].
The objectives of this study were to provide insights into the re-
tention and transport behavior of indium and gallium organic com-
plexes in porous media that are representative of some groundwater
environments. Trisodium citrate was used a as complexation agent that
stabilizes indium and gallium in solution; it is a naturally prevalent
molecule representative of short-chain organic acids present in soil.
Study of this system is a crucial step towards fuller understanding of the
environmental fate of these elements. Quartz sand was chosen as a
simple model porous medium. Sorption equilibrium tests were first
performed and interpreted in terms of Langmuir and Freundlich sorp-
tion isotherms. Transport behavior in saturated quartz sand columns
was then studied, with examination also of the effect of humic acid
(HA) – representative of natural organic matter – on indium and gal-
lium mobility. Because of the hydrolysis of indium(III) and gallium(III)
in a pH range typical of sand and soils, indium(III) and gallium(III)-
organic acid complexes are not expected to be significant [1]. However,
indium(III) and gallium(III) are known to form relatively strong poly-
nuclear complexes with α-hydroxyl acids in acidic media [27]. More-
over, HAs are known to form complexes with metal ions [28–30] and
they can thus influence significantly the binding and transport behavior
of metal ions in aqueous environments [30–32]. It is further noted that
citrate is an extremely soluble low molecular weight organic acid [33],
whereas humic acid has a much higher molecular weight, is far less
soluble (particularly under acidic conditions), and is frequently found
in colloidal material [34]. Hence, their roles in these experiments are
almost mutually exclusive. Finally, quantitative numerical modeling of
the experiments confirmed the factors controlling the retention of in-
dium and gallium.
2. Materials and methods
2.1. Materials
Indium(III) chloride (InCl3 98%), gallium(III) nitrate hydrate an-
hydrous basis (Ga(NO3)3·H2O 99.9%), trisodium citrate dihydrate
(C6H5Na3O7·2H2O), sodium bromide (NaBr ≥99.5%), hydrochloric
acid (HCl ≥37%), nitric acid (HNO3 70%), and humic acid (HA) so-
dium salt were purchased from Sigma-Aldrich (for more information on
the HA, see Section 3 in the SI). Medium size sand (UNIMIN, USA) was
used in all experiments (for more information on the sand, see Section 3
in the SI). Cobalt (10 mg/L stock solution) was purchased from
Inorganic Ventures and used as an internal standard in analytical
measurements. All solutions were prepared using double deionized
water (DDW, 18.2 MΩ cm).
2.2. Stock solution
Indium and gallium complexes with added trisodium citrate dihy-
drate, hereafter referred as citrate, were found to produce stable com-
plexes in aqueous solutions. Citrate is a typical component of soil or-
ganic matter and often used as a model molecule, for small natural
organic ligands, that are prevalent in the subsurface environment and
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Journal of Hazardous Materials 363 (2019) 394–400
interact with various metals [35]. All working solutions that are de-
scribed hereafter were prepared from stock solutions of 10 mg/L indium
or gallium, including citrate, and referred to hereafter as indium or
gallium solution. A molar ratio of 1:4.5 metal to citrate was shown to
yield stable complexes in aqueous solution and was thus applied in all
cases. For solutions that contain HA, the above working (stock) solu-
tions were mixed with 10 mg/L HA.
2.3. Sorption isotherms
Sorption equilibrium experiments were performed to quantify the
mass of indium and gallium that adsorbs to sand under equilibrium
conditions. Full details of these experiment protocols, and the results
and interpretation, are described in the Supporting Information (SI).
2.4. Column experiments
Transport behavior of indium and gallium was studied by vertical
sand column experiments. The experiments were carried out in dupli-
cates with solution concentrations of 1 mg/L metal and a molar ratio of
1:4.5 metal to citrate, or subsequently also including 10 mg/L of HA
(which is considered a common environmental level). In addition, each
stock solution contained 500 μg/L bromide (NaBr) which served as a
nonreactive tracer. All relevant figures depict the ratio of inlet con-
centration to measured outlet concentration C/C0 vs. pore volume (PV;
1 PV = total volume of fluid in the column).
Two polycarbonate columns with lengths of 18.2 cm and 19 cm, and
inner diameter of 3 cm were used. Each packed column underwent a
24 h saturation phase, which involved saturation with DDW, from the
bottom of the column, via a peristaltic pump to displace air in the pores.
The DDW reservoir was then substituted by a reservoir solution with the
respective metal complexes, and fraction collection at the column outlet
began. After running the experiment for 90–130 pore volumes, the re-
servoir was switched back again to DDW. For the entire experiment, the
pump delivery rate was 1.1 mL/min.
The pH of each collected sample was measured online with an
electrode placed at the outlet of each column. The pH was stable and
comparable within less than 0.25 pH units for all experiments as shown
in Figs. S3–S5.
2.5. Concentration analyses
All samples were analyzed via ICP-MS (Agilent 7700 s) for indium,
gallium and bromide concentrations. Before measurement, each sample
was filtered through a 0.45 μm PVDF (polyvinylidene fluoride) mem-
brane and then diluted with nitric acid, resulting in a total acid content
of 2%.
2.6. Modeling
The transport of indium and gallium complexes was quantified
using the software package Hydrus 1D [36], which can model transport
and retention of multiple solutes in water-saturated porous media. An
inverse mode was applied to fit sorption parameters to experimental
breakthrough curves (BTCs), using a nonlinear least squares optimiza-
tion routine, to evaluate the relevance of various nonequilibrium ki-
netic sorption models. Fits of tracer BTCs to the advection-dispersion
equation, associated with each indium or gallium transport experiment,
were used to obtain the dispersivity. Water content and bulk density
were calculated from gravimetric measurements and the geometry of
the column. For these simulations, steady state, uniform flow through a
saturated column was assumed. The effect of more complicated flow
behavior, such as mobile and immobile water, was neglected in this
study. Full details of the models are described in the SI.
K. Ringering et al.
Fig. 1. Breakthrough curves of bromide tracer ( ) compared to indium ( ) and
gallium ( ) citrate complexes in sand column experiments. Dashed grey line
represents the beginning of the flushing phase.
3. Results and discussion
3.1. Transport of indium and gallium
A set of BTCs for the column experiments with indium and gallium
citrate complexes and bromide tracer are presented in Fig. 1, showing
relative concentration as a function of pore volume. For clarity only one
BTC is shown here for each case; replicates demonstrating very similar
behavior are shown in the SI. The BTCs display typical sigmoidal pro-
gression during the first pore volumes, increasing until equilibrium
conditions are reached. Note that the initial breakthrough and sub-
sequent increases in indium and gallium concentrations are much
slower than those of the (nonreactive) bromide tracer, which show
classical behavior and elutes around 1 PV. It is further noted that for all
cases the first signs of elution of indium and gallium appear at 1 PV;
indium transport is particularly slow, and reaches equilibrium near C/
C0 = 0.8, while gallium elutes much faster and reaches equilibrium
near C/C0 = 0.95. The drop in all three BTCs (at about 130 PVs)
marked by the dotted line indicates the end of injection of the metal
solutions. Throughout the experiment, the pH values of the indium and
gallium solutions were similar with plateau at 6.4 ± 0.1, as shown in
Fig. S5.
The retention of indium and gallium in the columns can be char-
acterized via a retardation factor Rf, which quantifies the extent of in-
teractions between the respective solute and the sand matrix [37]. This
factor was calculated as the ratio of the number of pore volumes re-
quired for the metal to reach half of its equilibrium concentration, as
compared to that of bromide. The retardation factors were Rf = 31.2
and 30.5 for indium, and Rf = 6.0 for gallium, for each of the two
replicates of the column experiments, thus indicating good experi-
mental reproducibility in terms of the column transport parameters.
Note that, as background, measurements of sorption isotherms and
their interpretation, in equilibrium experiments, appear in Section 2 of
the SI. Briefly, for gallium, the resulting parameter values for the
Langmuir model are total number of binding sites, ST = 8.8 mg/kg and
Langmuir adsorption constant, KL = 6.9 L/mg, with a sum of squared
deviations (SSD) of 5.5. Fits with the Freundlich model yielded values
of free parameters KF = 9.2 mg/kg and n = 0.4, with SSD = 1.7. Based
on the SSD, the Freundlich model provides a better fit than the Lang-
muir model (Fig. S2A); these results suggest that the gallium sorption
on quartz sand may involve multilayer deposition and/or interaction
among sorbed species. For indium, the resulting Langmuir model
parameter values are ST = 8.2 mg/kg and KL = 57.0 L/mg with
SSD = 4.0, while the Freundlich model parameter values are
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Journal of Hazardous Materials 363 (2019) 394–400
KF = 10.7 mg/kg and n = 0.3 with SSD = 3.4. As for gallium, the
Freundlich model for indium provides a better fit (Fig. S2B).
Following the switch from the injection phase experiments to their
flushing (desorption) phases (marked as a dashed line in Fig. 1; recall
Section 2.4), the indium concentration decreased rapidly, similar to
that of bromide. This behavior implies that of the total mass of indium
that was retained in the column during the retention phase, indium is
not released during flushing of the column with DDW. In comparison, a
long tail over many PVs is observed for the gallium, indicating rela-
tively slow release of gallium during the flushing phase; note that the
experiment ended prior to complete release of all the retained gallium.
Comparison of the indium and gallium BTCs shown in Fig. 1 in-
dicates different transport and retention behaviors under similar con-
ditions. Indium shows a much greater degree of retardation than gal-
lium, which is represented by its higher Rf value. Moreover, the
retention of indium appears to be irreversible. The tailing pattern (with
the onset of flushing) of indium and the inert (nonsorbed) bromide
tracer suggests that no retained indium is desorbed once its injection is
stopped. These findings suggest that the interactions of indium with the
quartz sand surface are stronger than those of gallium. This result is
somewhat surprising, given that relative to indium, gallium has a lower
ionic radius (0.47 Å and 0.62 Å for Ga3+ and In3+, respectively [38])
and a stronger ionic potential (ratio of ionic charge to ionic radius). Bi
and Westerhoff [10] demonstrated, for these elements, differences in
chemisorption potential with speciation and higher tendency to form
bonds under acidic conditions with positively charged SiO2 surface.
A possible explanation for this result is that at pH 6.5, speciation
calculations (see Section 4 SI and Fig. S3) indicate that In(III) is present
as In(OH)3aq, which can lead to formation of hydrogen bonds with the
quartz surface sites. Under the same conditions, Ga(III) is present
mostly as Ga(OH)4− leading to electrostatic repulsion with the quartz
sites that are negatively charged. Additionally, citrate complexation
with each of the elements can alter the retention dynamics. Two pos-
sible, different behaviors of the BTC experiments can thus be expected:
competition between citrate and quartz sand to complex the metal, and
a ternary system where the metal can be bound to citrate and quartz
simultaneously. Ivanova et al. [27] found that indium(III) citrate and
indium(III) hydroxo complexes are not as stable as similar gallium(III)
complexes. Hence, it might be hypothesized that the lower amount of
retained gallium, and its lower retardation factor as exhibited in the
BTC, are caused by a greater stability of gallium citrate complexes,
which lead to weak binding of gallium on the sand surface. In contrast,
the weaker indium citrate complexes can be broken up, forming other
less stable indium species in solution, or In(OH)3s that precipitates on
the sand surface, leading to preferential, irreversible retention of in-
dium in the sand column. These differences in stabilities of indium(III)
and gallium(III) complexes, and the behavior of the BTCs suggest a
competition mechanism between the organic ligand and the mineral
surface. This competition mechanism is supported by Schwab et al.
[39], who showed that citrate was adsorbed to soil and influence the
adsorption of lead on a soil composed of 35% sand, 42% silt, 23% clay,
and 15 g/kg of organic carbon. The sorption of lead onto the soil was
reduced due to the presence of Pb-citrate complexes in solution. A
competition mechanism between the organic ligand and the soil was
therefore assumed similarly to the current study. Citrate was also
shown to increase the leaching of iron and aluminum from soils
[40,41], thus competing with metals sorbed on soils.
3.2. Indium and gallium transport in the presence of humic acid
The BTCs in the experiments with indium (Fig. 2) show very dif-
ferent behavior for transport of indium without and with the presence
of HA. BTC patterns, in the presence of HA, also indicate different be-
havior for indium as compared to gallium (Figs. 2 and 3). In Fig. 2, the
BTC for indium with HA shows significantly higher mobility than for
indium without HA. The retardation factor for indium with HA
K. Ringering et al.
Fig. 2. Breakthrough curves comparing bromide tracer ( ) and indium in the
presence ( ) and absence ( ) of 10 mg/L humic acid (HA), and fits of the
attachment/detachment (red and blue solid lines) and chemical nonequilibrium
(red and blue dashed lines) models to each curve (For interpretation of the
references to colour in this figure legend, the reader is referred to the web
version of this article).
Fig. 3. Breakthrough curves comparing bromide tracer ( ) and gallium in the
presence ( ) and absence ( ) of 10 mg/L humic acid (HA), and fits of the
attachment/detachment (red and blue solid lines) and chemical nonequilibrium
(red and blue dashed lines) models to each curve (For interpretation of the
references to colour in this figure legend, the reader is referred to the web
version of this article).
(Rf = 18.7 and 19.4) is much lower than without (Fig. 2; Rf = 31.2 and
30.5). In contrast, the BTCs for gallium in the presence of HA are quite
similar to those for gallium without addition of HA (see Fig. 3). How-
ever, comparison of the Rf values indicates greater retardation in ex-
periments with HA (Rf = 8.1, 7.0) than in experiments without it (Rf =
6.0). This finding is somewhat surprising, given that the presence of HA
generally increases metal mobility and reduces sorption [e.g., [42]]. It
is noted that throughout the experiment, the pH of indium with and
without addition of humic acid was similar, with plateau at ∼6.5 as
shown in Fig. S4.
The adsorption of HA onto quartz sand and/or the competition
between HA and citrate, both acting as ligands, are expected to alter the
retention dynamics of both indium and gallium onto quartz. However,
397
Journal of Hazardous Materials 363 (2019) 394–400
because both indium and gallium are part of group 13 in the periodic
table, and located one directly above the other, similar trends in their
transport behavior might be expected. The pronounced difference in
transport behavior and interaction with HA requires further discussion.
Hereafter, the possible explanations for the behavior of each element
are examined.
3.2.1. Effect of humic acid on indium transport
For the experiments with indium, the most striking difference is in
the shape of the BTCs, which changed from a sigmoidal shape in the
absence of HA, to a strictly convex shape in the presence of HA (Fig. 2).
Clearly, the initial uptake of indium is much lower in the presence of
HA, which is also reflected by a lower retardation factor. HA is capable
of binding and stabilizing the indium [43] and is also known to sorb on
quartz surfaces [32,44,45]. The speciation of indium (and gallium) has
received little attention but several studies show that aluminum – in the
same column in the periodic table – forms complexes with HA [46–50].
Therefore, indium and gallium are also expected to form complexes
with HA. It is further noted that from the speciation calculations shown
in Section 4 of the SI, In(III) is predicted to be bound mostly to HA
(∼90%) in the inlet solution, as shown in Fig. S4B. Therefore, in the
presence of HA, indium can be expected to react and form indium-HA
complexes that stabilize the dissolved indium fraction in the aqueous
solution. Moreover, in the column experiments, indium complexes must
compete with HA molecules for binding sites on the quartz sand sur-
faces. This effective reduction in available binding sites for indium can
cause a slowdown in the sorption kinetics, which would also be in ac-
cord with the observation of a reduced fraction of retained vs. injected
mass during the retention phase (Fig. 2).
If the binding affinity of HA to the sand is weaker than that of the
indium complexes the binding sites that are blocked by HA become free
after some time. These binding sites are then occupied by indium. As
this means that the retention of indium effectively proceeds more
slowly than in the absence of humic acid, the equilibrium is reached at
higher pore volume values. The result is a situation wherein the total
amounts of binding sites occupied by indium are eventually similar
under both experimental conditions. The plateau phase of the BTC in-
dicates that either all sorption sites are occupied or that the system has
reached equilibrium. The presence of HA stabilizes the dissolved in-
dium in the solution; as a result, a smaller fraction of dissolved indium
undergoes transformations such as precipitation, which leads to a
higher steady state solution concentration and higher plateau level
(Fig. 2).
3.2.2. Effect of humic acid on gallium transport
In contrast, the presence of HA has a much smaller impact on gal-
lium mass retention and release, relative to indium. The shape of the
BTCs does not change notably with the addition of HA (Fig. 3). How-
ever, in the presence of HA, retardation increases slightly and a higher
fraction of gallium injected mass is retained during the retention phase.
The difference between transport of gallium in the presence and ab-
sence of HA in the range between 6 and 12 PVs, where the two curves
split, is statistically and experimentally significant; see Fig. S10 and
Section 6 in the SI. However, when considering the overall behavior of
gallium and the environmental implications, the effect of HA in the case
of gallium is minimal. Note also that the retardation factors in this case
are calculated (by definition) exactly in the zone of the largest gap
between the curves, so that Rf emphasizes the effect of HA which for
most parts of the BTC is not significant. Much of this retained mass is
subsequently released during the flushing phase, regardless of the
presence of HA. Clearly, the mechanisms discussed above for indium
retention onto quartz, regarding the role of HA, do not apply for gal-
lium. For this case too, throughout the experiment, the pH values of
gallium with and without addition of humic acid overlap almost com-
pletely, with a plateau at ∼6.4 as shown in Fig. S5.
The retention of gallium, both in the presence and in the absence of
K. Ringering et al.
HA, is reversible, implying a weaker binding between gallium com-
plexes and the sand surface regardless of the exact type of complex
formed by gallium in each case. It was shown previously that gallium
forms strong complexes with small organic ligands [27]. Hagvall et al.
[51] studied the coordination of gallium(III) in the presence of natural
organic matter (Suwannee River Natural Organic Matter and Suwannee
River Fulvic Acid) using EXAFS and infrared spectroscopy. These au-
thors found that mononuclear complexes between gallium(III) and
carboxylate sites of natural organic matter are predominant for acidic
to neutral media. When the pH increases, gallium(III)-HA mononuclear
complexes tend to break up and yield Ga(OH)3s, which can then interact
with carbohydrates. At the lowest studied concentration (0.3 mmol
gallium(III)/mol R-COOH), EXAFS showed that the contribution of the
second-shell C atoms became more important. This finding can be in-
terpreted as the formation of gallium(III)-NOM cage-like structures,
although further study is needed to describe these structures. The case
of the coordination of gallium in a ligand shell might not allow for
direct interaction with the sorbent, resulting in relatively weak bonding
[52]. Obviously, the presence of HA does not have an inhibitory effect
on the retention of gallium onto sand, which can be seen in its slightly
higher retardation factor as compared to experiments without HA.
Gallium, being a strong complexation center, forms complexes not
only with citrate, but also with HA [e.g., [53]]. However, Takahashi
et al. [54] reported that the behavior of gallium sorption to kaolinite is
largely unaffected by the presence HA. In these experiments, gallium
was preferentially sorbed on the mineral surface. Moreover, when
gallium was sorbed on the mineral surface in a gallium(III)-kaolinite
binary system, these authors reported that ∼10% of the gallium(III)
was partitioned to the dissolved phase in the pH range of 5–7, in the
presence of HA. It is further noted that at the beginning of the experi-
ments, the gallium(III) in solution is complexed to the carboxylic sites
of the citrate. While the gallium citrate complex is strong, a small
amount of gallium can be released and react with the carboxylic sites of
the HA, which are the major sites involved in the complexation of
gallium(III) in this pH range [51]. It is noted that in the inlet solution,
Ga(III) is predicted to be bound to citrate (∼35%) and to HA (∼63%)
at pH 5.5 (Fig. S2). When the pH increases to 6.5, Ga(III) is present as
Ga(OH)4− and Ga-HA (respectively 45.7 and 53.7%) and Ga(OH)3s is
predicted to precipitate. In these BTC experiments, gallium can sorb to
the sand surface either in form of a citrate complex and/or as a HA
complex, but this will not cause a substantial change in the retention
pattern or magnitude.
A comparison of the complexation behavior of indium and gallium,
both belonging to group 13 in the periodic table, to the most-studied
element of the same group - aluminum - provides some interesting in-
sights. A review of the fate of aluminum in aqueous environments
highlights that the type of complexation can even differ for the same
species of metal ion under different conditions [29]. Aluminum forms
complexes with HA either in the form of outer-sphere complexes, or in
the form of inner-sphere complexes, depending on the chemical para-
meters such as the presence of competing ions, the ionic strength and
pH value of solutions. Whether inner- or outer-sphere complexes are
formed can in turn lead to fundamentally different interactions between
the complexes and charged surfaces.
3.3. Modeling
Two kinetic sorption models were applied to simulate the transport
behavior of indium and gallium: attachment/detachment model (Eq.
(5), SI) and chemical nonequilibrium sorption (Eq. (7), SI). Simulation
results are shown in Figs. 2, S8 and S9 for indium experiments and
Figs. 3, S10 and S11 for gallium experiments. To reduce the number of
free parameters, the maximum number of retention sites, Smax, was
assumed to be unaffected by the experimental conditions, and its value
was fixed throughout the entire set of attachment/detachment simu-
lations. Similarly, the Freundlich parameters, KF and n, which describe
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Journal of Hazardous Materials 363 (2019) 394–400
the equilibrium sorbed concentration, were fixed separately throughout
each set of indium and gallium transport simulations (see Smax, KF and n
in Table S1). Moreover, the detachment rate was set to zero for all in-
dium simulations because no desorption was observed.
The plateau phase of the BTC represents an equilibrium or steady-
state phase of the retention process. A plateau at C/C0 < 1 is governed
by additional processes represented by (eq. (4), SI), which is de-
termined by the rate constant, μ (for both models). The fitted values for
μ indicate higher inactivation rate of indium than gallium, in the ab-
sence of HA. This leads to a lower plateau level, consistent with the
observation shown in Fig. 2. The effect of HA on indium stabilization is
reflected by a decrease in the inactivation rate constant. Consequently,
an elevated plateau level is established, as shown in Fig. 2 (compare μ
values for indium in the presence and absence of HA in Table S4). In
contrast, the presence of HA had an insignificant effect on gallium
transport behavior. The similar plateau levels in all gallium experi-
ments, regardless of the presence of HA (Figs. 3, S10, and S11), de-
monstrate comparable values of the inactivation rate constants.
The fitted attachment rate constants are larger for indium than for
gallium, ka-indium > ka-gallium, accounting for the higher retention of in-
dium in the column. Similarly, ka indium > ka indium, HA, indicating the
effect of HA on indium retention.
The chemical nonequilibrium sorption model involves three reten-
tion parameters, k , KF and n (Eqs. (2), (7), SI). The model results re-
turned k indium < k gallium , which is counter-intuitive because indium
was retained in the column to a significantly greater degree than gal-
lium. However, in (Eq. (7), SI), the parameter k controls both the
sorption and desorption rates; because desorption of indium was neg-
ligible and desorption of gallium was substantial, the k value for in-
dium was minimized. To compensate, the retention parameter, KF, was
larger for indium as compared to gallium.
As discussed above, gallium-citrate complexes are relatively strong
and stable in solution, so that gallium transport is governed mostly by
the direct interaction of gallium-citrate with the sand surface, regard-
less of the presence of HA. Both models captured the experimental
measurements with R2 > 0.88, as shown in Fig. 3 and Table S4.
The quantitative analyses of indium BTCs are shown in Fig. 2. Un-
like gallium, indium shows larger retention and is affected significantly
by the presence of HA. The attachment/detachment model exhibits
better performance, compared to the chemical nonequilibrium sorption
model, with regard to simulating indium transport. The latter mainly
failed to capture the S shape of the retention phase of the BTC, and the
sharp decrease to background (zero elution) concentration level of the
BTC tail. On the other hand, in the presence of HA, the attachment/
detachment model predicts a small sharp increase of indium con-
centration at the initial breakthrough, which is not observed in the
experiments.
As discussed in Section 3.1, indium forms relatively weak complexes
with citrate, so that the total retention of indium may involve a larger
extent of metal species other than indium-citrate. In addition, deso-
rption of indium, following the retention phase, was not observed.
Often, for metal species on soil surfaces, rates of desorption are con-
siderably slower than rates of adsorption [e.g., [55]]. A possible ex-
planation is that the sorbed citrate complex is transformed, enabling
direct interaction of indium or indium hydroxide with the sand surface;
such interaction is strong, and practically irreversible for the conditions
of this experiment. This mechanism may be stronger for indium than for
gallium, due to the different stability of the metal-citrate complex. In
such a mechanism, the sorption of indium is: (1) limited by the max-
imum sorption sites for indium ions (related to the cation exchange
capacity of the sand), rather than the equilibrium between sorbed and
aqueous indium-citrate complex; and (2) described by independent
sorption and desorption rates (desorption is practically minimized).
Therefore, the attachment/detachment model is preferred here.
Overall, for indium, when the metal is stabilized, i.e., when HA is
added to the system, there is one major complex that is transported
K. Ringering et al.
through the column. In such a case, both nonequilibrium and attach-
ment/detachment models describe the BTC adequately. When the
system is less stable and multiple complexes can be formed and mobi-
lized, the attachment/detachment model better describes the transport.
This is due to the independence of the sorption and desorption pro-
cesses in the model. When there are more possibilities that the complex
will react and then be transformed – e.g., when a sorbed complex reacts
while being sorbed to form different species that show lower desorption
rates – breaking the link between sorption and desorption can be ad-
vantageous as each phase is independent of interactions of the other
phase. For gallium, the citrate complex is relatively stable and is not
affected by the presence of HA; thus the system is more stable and both
models can describe the transport behavior.
4. Conclusion
The objectives of this study were to provide insights into the re-
tention and transport behavior of indium and gallium organic com-
plexes in porous media that are representative of some groundwater
environments. The use of both elements has grown almost ex-
ponentially since the early 2000s, resulting in their increased, un-
avoidable, release to the environment. Therefore, better constraints on
the potential of indium and gallium to migrate in the subsurface and
contaminate water reservoirs are needed critically.
Here it is shown that indium and gallium demonstrate similar
sorption patterns, with the Freundlich isotherm (multilayer, equili-
brium dependent) yielding somewhat better fits to the observations
than the Langmuir isotherm (monolayer sorption). However, indium
shows much stronger adsorption parameters. The transport behaviors of
indium and gallium were found to be very different, however, with
gallium being more mobile and less affected by the addition of HA.
Therefore, indium appears to pose a lower risk of travelling through
waterways and entering drinking water, relative to gallium. However,
indium is much more sensitive to the presence of HA in solution; even
levels of 10 mg/L can lead to very large changes in the pattern, rate and
amounts of indium transported in porous media. This may indicate the
potential that other components found in the aqueous solution may
affect the mobility of both elements in the porous medium, due to their
different reactivity, competition or even different speciation. The sig-
nificant differences in the behavior of the two metals are explained by
the strength of the complexes they form, and in turn the potential in-
teractions of the complex with other substances in the system (such as
other ligands or charged surfaces).
Modeling of the BTCs of both indium and gallium confirmed the
suggested complexation behavior, which explains the major differences
observed for the mobility of the two elements and the effect of the
presence of humic acid in solution on their transport. The modeling also
suggests that when the composition of solution is stable and the spe-
ciation of the complexes remains constant, both nonequilibrium and
attachment/detachment models can describe the transport. When the
solution composition in the system is changing and a substance can be
transformed to different species, decoupling the sorption and deso-
rption processes is advantageous. This study provides initial informa-
tion regarding the transport behavior of both elements, but further
research that considers more reactive porous media, more complex
solution compositions, and different conditions (including effects of
acidity and other ligands) should also be considered.
Competing interests statement
The authors have no competing interests to declare.
Acknowledgements
B.B. gratefully acknowledges the support of research grants from the
Crystal Family Foundation, from Rochelle Rubinstein and Ms. Darlene
399
Journal of Hazardous Materials 363 (2019) 394–400
Switzer-Foster and Mr. Bill Foster, and from the De Botton Center for
Marine Science. B.B. holds the Sam Zuckerberg Professorial Chair in
Hydrology.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jhazmat.2018.09.079.
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