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3-2016

Removal of Cu (II) and Pb (II) from Aqueous Solution using

engineered Iron Oxide Nanoparticles
Carlos Tamez
The University of Texas Rio Grande Valley

Rebecca Hernandez
The University of Texas Rio Grande Valley

Jason Parsons
The University of Texas Rio Grande Valley, [email protected]

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Recommended Citation
Tamez, C., Hernandez, R., & Parsons, J. G. (2016). Removal of Cu (II) and Pb (II) from Aqueous Solution
using engineered Iron Oxide Nanoparticles. Microchemical journal : devoted to the application of
microtechniques in all branches of science, 125, 97–104. https://doi.org/10.1016/j.microc.2015.10.028

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Microchem J. Author manuscript; available in PMC 2017 March 01.
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Published in final edited form as:

Microchem J. 2016 March 1; 125: 97–104. doi:10.1016/j.microc.2015.10.028.

Removal of Cu (II) and Pb (II) from Aqueous Solution using

engineered Iron Oxide Nanoparticles
Carlos Tamez, Rebecca Hernandez, and J. G. Parsons*
Department of Chemistry, University of Texas Rio Grande Valley, 1201 W University Dr. Edinburg
TX 78539
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Abstract
Nano-sized Fe3O4 and Fe2O3 were synthesized using a precipitation method. The nanomaterials
were tested as adsorbents for the removal of both Cu2+ and Pb2+ ions. The nanomaterials were
characterized using X-ray powder diffraction to determine both the phase and the average grain
size of the synthesized nanomaterials. Batch pH studies were performed to determine the optimum
binding pH for both the Cu2+ and Pb2+ to the synthesized nanomaterials. The optimum binding
was observed to occur at pH 4 and above. Time dependency studies for Cu2+ and Pb2+ showed the
binding occurred within the first five minutes of contact and remained constant up to 2 hours of
contact. Isotherm studies were utilized to determine the binding capacity of each of the
nanomaterials for Cu2+ and Pb2+. The binding capacity of Fe3O4 with Cu2+ and Pb2+ were 37.04
mg/g and 166.67 mg/g, respectively. The binding capacities of the Fe2O3 nanomaterials with Cu2+
and Pb2+ were determined to be 19.61 mg/g and 47.62 mg/g, respectively. In addition, interference
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studies showed no significant reduction in the binding of either Cu2+ or Pb2+ to the Fe3O4 or
Fe2O3 nanomaterials in the presence of solutions containing the individual ions Na+, K+, Mg2+
and Ca2+ or a solution consisting of a combination of all the aforementioned cations in one
solution.

Keywords
Copper; Lead; iron oxide nanomaterials; sorption; XRD; ICP-OES

1. Introduction
Contamination of potable water is a major global environmental and human heath concern
as more and more countries become industrialized. Both copper and lead are of interest due
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to numerous health concerns associated with exposure to these heavy metals. At low
concentrations, lead has been shown to affect the nervous and renal systems; lead has been
shown to negatively affect the synthesis of heme (1,2). Exposure to high levels of copper has
been associated with liver damage nausea, abdominal pain, diarrhea, and vomiting (3).

*
Corresponding Author: Phone (956)-665-7462, [email protected].
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 Tamez et al. Page 2

Many common industrial processes such as battery manufacturing, battery recycling, paint
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manufacturing, metal smelting, oil refining, mining, electroplating, and the manufacturing of
alloys; produce large amounts of copper and lead contaminated waste. Disposal of copper
and lead contaminated wastes have been shown to contaminate natural clean water (4, 5).
Heavy metal contamination is of a concern due to the difficulty of the remediation of heavy
metals from soils (1).

Various methods have been studied for the removal of heavy metal ions, which include: ion
exchange, biosorption, activated carbon sorption, solvent extraction, precipitation,
coagulation, and adsorption (6, 7). Although these methods have been shown to be effective
for the remediation of heavy metals, many of the aforementioned methods are either costly
or complicated to implement. Adsorption, on the other hand, is relatively inexpensive and
easy to implement. The use of nanometer-sized adsorbents has the advantage of higher
surface area for increased reactivity (8) Recent studies have shown that nano-sized Fe3O4
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and Al2O3 were effective for the removal of lead, with Fe3O4 having a higher binding
capacity than the Al2O3 (9). A second study showed that Fe3O4 had a binding capacity 10
times higher for copper and lead than a CuO nanomaterial (10). The use of Fe3O4
nanomaterials have the added benefit of superparamagnetism and can be easily removed
using a magnet, thus the removal of contaminates can be achieved using magnets/magnetic
fields.

In this study nano-sized Fe3O4 and Fe2O3 were synthesized using a titration/precipitation
method. The method involved the titration of solutions of iron(III) chloride or iron (II)
chloride with sodium hydroxide. The resulting nanoparticles were characterized using X-ray
diffraction to determine their crystal structure and average grain size. The nanomaterials
were then investigated for their potential as adsorbents for Cu2+ and Pb2+ in solution. Batch
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studies were performed to determine the optimum binding pH, equilibration time, and
binding capacity. The binding capacity studies were performed using isotherm studies and
found to follow the Langmuir isotherm. In addition, the effects of K+, Na+, Ca2+, and Mg2+
ions on the binding of both copper and lead were also investigated at the optimal binding
pH.

2. Experimental
2.1. Synthesis of iron nanomaterials
Fe3O4 and Fe2O3 was synthesized via a slow titration/precipitation method. Fe3O4 was
synthesized using a 1.0 L 30 mM solution of iron (II) chloride, which was titrated drop wise
with 100 mL of 1 M sodium hydroxide. The 30 mM iron (II) chloride was prepared by
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dissolving 30 mmol (5.964 g) of iron (II) chloride in 1.0 L of 18 MΩ Millipore water. The
Fe2O3 nanomaterial was synthesized using the same method a 1.0 L 30 mmol of iron (III)
chloride was titrated using 100 mL of 1 M sodium hydroxide. The 30 mM FeCl3 solution
was prepared by dissolving (8.109 g) of iron (III) chloride in 1 L of 18 MΩ Millipore water.
The 1 M sodium hydroxide was prepared by dissolving 40.0 g of sodium hydroxide in 18
MΩ Millipore water. The titration of the iron(II) and iron(III) solutions was performed at
rate of 1 mL min−1 under vigorous stirring. Subsequent to the addition of the NaOH to the
iron solutions the samples were boiled for 1 hr under vigorous stirring. The solutions were

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then cooled to room temperature, centrifuged at 3500 rpm for 5 minutes, decanted,
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suspended again in 18.0 MΩ deionized water centrifuged. The nanomaterials were washed
three times using 18.0 MΩ deionized water followed by centrifugation to remove any by-
products and unreacted starting material. The resulting nanoparticles were oven dried
overnight at 70°C.

2.2. Characterization of iron nanomaterials

The synthesized Fe3O4 and Fe2O3 nanomaterials were characterized using a Rigaku
Miniflex XRD equipped with a scintillation detector. The samples scans were collected from
20° to 60° (2θ) with a count time of 1 s and a step of 0.01° in 2θ. The resulting diffraction
patterns were then fitted using the Le Bail fitting procedure and crystal structure data from
the literature (11, 12). The Average grain size of the nanoparticles was determined using
Scherrer’s equation and the full width at half maximum of three independent diffraction
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peaks.

2.3. pH study
Stock solutions of either Cu2+ or Pb2+ were prepared at concentrations of 300 ppb. The pH
of the stock solutions were adjusted to 2,3,4,5, 6 using either dilute nitric acid or dilute
sodium hydroxide. From the pH adjusted stock solutions 4 mL aliquots of the solution was
then placed into 5 mL tubes, which were preloaded with 10 mg of either Fe3O4 or Fe2O3
nanomaterials. In addition, control reactions were also maintained for all reactions, which
consisted of 4 mL aliquots of the Cu2+ or Pb2+ solutions without the nanomaterials. All
samples and control reactions were performed in triplicate for statistical purposes. The tubes
were capped and placed on a speci-mix rocker and equilibrated for 1 hr. After equilibration
the tubes were centrifuged for 5 min at 3000 rpm, decanted, and saved for analysis. Metal
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analysis was performed using a PerkinElmer AAnalyst 800 atomic absorption spectrometer
operated in graphite furnace mode. All calibration curves obtained for analysis had
correlation coefficients (R2) of 0.99 or better.

2.4. Time Dependency Studies

Samples consisting of 10mg of either Fe3O4 or Fe2O3 were weighted out and placed in 5 mL
tubes and 4 mL aliquots of pH adjusted (pH 4) 300 ppb solution of either Cu2+ or 300 ppb
Pb2+ were added to the tube. The tubes were then capped and equilibrated for the following
times: 5,10, 15, 20, 30, 60, 120, and 240 min. Control samples consisting of either the Cu2+
or Pb2+ ions, without the iron oxide nanoparticles were maintained and treated the same as
the reaction samples. All samples and controls were performed in triplicate for statistical
purposes. After equilibration the test tubes were centrifuged for 5 min at 3000 rpm,
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decanted, and the supernatants were saved for analysis. A PerkinElmer AAnalyst 800 atomic
spectrometer was used to analyze the samples. Cu2+ and Pb2+ concentrations were
determined using calibration curves with correlation coefficients (R2) of 0.99 or better.

2.5. Adsorption isotherm

Isotherm studies were performed under similar conditions as the time dependency studies,
with the exception of a fixed 1 hr equilibration time. Solutions of Cu2+ and Pb2+ at the

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following concentrations: 5, 10, 50, 100, and 1000 ppm were adjusted to a pH 4. A 4.0 mL
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aliquot of the pH adjusted Cu2+ or Pb2+ solution was added to 5 mL test tubes, containing
either 10 mg of Fe3O4 or 10 mg of Fe2O3. The tubes were capped, equilibrated for 1 hr, and
centrifuged for 5 min at 3000 rpm. In addition, control samples consisting of either the Cu2+
or Pb2+ solutions were maintained through the equilibration time and treated the same as the
samples. The reaction sample and control samples were prepared in triplicate for statistical
purposes. Subsequent to centrifuging the supernatants were saved for analysis with a
PerkinElmer ICP-OES Optima 8300. Calibration curves with correlations coefficients (R2)
values of 0.99 or better were obtained for all analyses.

2.6. Binding interference

The effects of potential interference of secondary cations Na+, K+, Mg2+, and Ca2+ to Cu2+
and Pb2+ binding onto Fe3O4 and Fe2O3 was determined by preparing solutions of 0.3, 3,
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30, 300, and 3000 ppm of Na+, K+, Mg2+, and Ca2+ spiked with 300 ppb of either Cu2+ or
Pb2+. In addition, a mixture of all four cations was prepared with each cation at the
aforementioned concentrations in the presence of 300 ppb of either Cu2+ or Pb2+. All
solutions were pH adjusted to 4.0 and 4.0 mL aliquots were added to tubes containing 10 mg
of either Fe3O4 or Fe2O3. Control solutions were also prepared consisting of the mixture of
cations without the nanomaterials present. The test tubes were capped, equilibrated for 1 hr,
centrifuged for 5 min at 3000 rpm, decanted, and the supernatants were saved for analysis.
Analysis was performed using a PerkinElmer ICP-OES Optima 8300 using calibration
curves with correlations coefficients (R2) values of 0.99 or better.

3. Results
3.1. X-ray Diffraction of synthesized iron oxides
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The XRD patterns for the Fe3O4 and Fe2O3 synthesized are presented in Fig 1. Fig. 1A
shows the XRD pattern for Fe3O4 contains the 220, 311, 400, 422, and 511 Miller indices,
indicating that the magnetite phase was obtained (13). The observed Miller indices
correspond to the diffraction peaks observed at the following angles 30.11, 35.44, 37.11,
43.11, 47.11, 53.44, and 57.00 in 2θ. Fig. 1B shows the XRD pattern obtained for Fe2O3
synthesis which, contains the 111, 040, 113, 201, 202, 212, 214, and 006 Miller indices
corresponding to ε-Fe2O3 (14). The diffractions peaks were observed at the following angles
21.46, 33.58, 35.07, 36.91, 40.38, 41.59, 53.49, and 59.44 in 2θ. The fittings of the
diffraction patterns were performed using the Le Bail fitting procedure in the FullProf suite
and crystallographic data from the literature (10, 11).

The average grain size of each of the nanomaterials was calculated using Scherrer’s equation
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and the full width half maximum (FWHM) of three independent diffraction peaks.
Scherrer’s equation is provided below:

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Where d is the nanomaterials diameter, λ is the wavelength of the copper x-ray source (1.54
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Å), β is FWHM of the peak, and 2θ/2 is the diffraction angle. Using the Scherrer’s method
the average grain size of the synthesized Fe3O4 nanomaterial was 19.9 nm ± 0.2 nm,
whereas the synthesized Fe2O3 material had an average grain size of 12.9 nm ± 1.4 nm.
Luther et al., as well as Parsons et al., have observed similar results for iron oxide
nanomaterials synthesized using this precipitation technique (15–17). These authors have
shown nanomaterials synthesized through the precipitation technique have average grain
sizes of 17.0 nm (Fe3O4), 12 nm (Fe2O3), 28 nm (Fe3O4),, and 19 nm (Fe3O4).

3.2. pH binding studies

The effects of pH on the binding of copper and lead to Fe3O4 and Fe2O3 are shown in
Figure 2. Figure 2A shows the binding of copper and lead to Fe3O4 nanomaterial. As can be
seen in Figure 2A at pH values below 3, both Cu2+ and Pb2+ binding to the Fe3O4
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nanomaterial is very low, less than 15% and 5%, respectively. However, at pH 3 and above
the binding increased to greater than 90% for Pb2+. Cu2+ binding to the nanomaterials was
observed to increase with increasing pH. However, the maximum binding for the Cu2+ was
achieved at pH 4 and above. Figure 2B shows the binding of Cu2+ and Pb2+ to Fe2O3 from
pH 2 through pH 6. Cu2+ showed little to no binding at pH 2 and an increase to
approximately 80% binding at pH 3 and above. Similarly, observed Pb2+ binding to Fe2O3
was low at pH 2, below 20%, which increased to 80% at pH 3 and remained relatively
constant through pH 5. However, the Pb2+ binding was observed to decreased slightly to
approximately 65% at pH 6. The reduction in binding may have been due to Pb(OH)X
species formation, which have been observed to start forming at pH 5 and above (18). The
formation of the hydroxide species observed for Pb2+ in solution may inhibit to adsorption
of the Pb2+ ions to the surface of the nanomaterials. Similar studies have observed
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comparable results for the removal of lead (10, 19). However, Mahdavi et al, studying the
removal of heavy metal ions using Fe3O4, ZnO and CuO obtained less than 20% removal of
copper up to pH 6, with a drastic increase to nearly 100% at pH 7. Katsumata et al. found
effective removal of both copper and lead (over 90%) with Fe3O4 (20). Yu et al. observed
optimal binding of copper and lead at pH 4 using sawdust as the adsorbent (21). Machida et
al showed the adsorption of Pb2+ from aqueous solution using carbon based materials
occurred optimally at pH 5.5 (18). The selection of pH 5.5 as the optimal binding pH was
due to the speciation of the Pb2+ ions in solution. At pH 5.5 and below the majority of lead
ions in solution are present as the single hydrated lead ions (Pb2+) (18). Above pH 5.5
hydrated Pb species have been found to exist in solution, which may change the binding
properties of the ions (18).

3.3. Time Dependency Studies

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The results from time dependency studies are shown in Fig. 3. Fig. 3A shows the binding of
Cu2+ and Pb2+ to the Fe3O4 nanomaterials, as can be seen in Fig. 3A the binding was
independent of time. The Cu2+ solution concentration was reduced by approximately 90%
within the first 5 minutes of contact and remained constant up to 120 minutes of contact
time. However, a slight increase (approximately 10%) in the Cu2+ binding was observed at
the 240 minutes time interval. Similarly the Pb2+ binding remained relatively constant at
approximately 85% from the initial 5 minute contact time to 240 minute contact time. Fig.

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3B shows the binding of both Cu2+ and Pb2+ to the Fe2O3 nanomaterials. As can be seen in
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Figure 3B the Cu2+ binding remained below 70% for the first 15 min of contact time with
Fe2O3 and maximum binding was observed at 20 min, with little to no change up to the 240
minute contact time. Similarly, Pb2+ ions showed a small increase in binding percentage
binding at the 20 minute contact time. Initially the Pb2+ removal was observed to be
approximately 70% at 5 min and was observed to increase to approximately 90% at 20 min
and remaining constant through to the 240 min of contact time. The results obtained in this
study are significantly higher than previously conducted studies using Fe3O4. Mahdavi et
al., found between 40%–50% lead removal through 100 min of contact time, this value
increase to 60% lead removal at 120 min (10). Similarly, copper removal remained
approximately 40% through 120 min of contact time. A second study, achieved 35% after 2
h of contact with Fe3O4, with only a slight increase to 40% after 5 h of contact (8). The
observed differences in the percentage binding may be due to many different factors,
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primarily the concentrations at which the reactions were performed. In the present study 0.3
ppm of either Cu2+ or Pb2+ was used for primary investigations. However, many of the
comparable studies with respect to pH are in the ppm concentration ranges (18, 22–24). The
observed increase in the binding of metal ions from solution with increasing time has been
observed in the literature. Ions such as gold(III) show this phenomenon and it is generally
related to the reduction of the gold(III) ion to gold(0). The reduction of gold ions in solution
using many different biomasses has been highlighted in the literature (25,26). The reduction
of silver(I) ions in solution binding to biomass has also been shown using Basil and
Cinnamon zeylanicum bark(27,28). In addition, it has also been shown in the literature that
magnetite (Fe3O4) has the capability to reduce copper(II) ions as well as Vanadium(V), and
chromate ions (29). The observed increases in the adsorption of both the Cu2+ and Pb2+ ions
at the 20 minute contact time may be due to a change at the surface after complexation of
the ions. Alternatively, on the surface of the Fe2O3 residual protons may be blocking the
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binding of the metal ions, once the protons are removed then the binding of the Cu2+ and
Pb2+ may occur.

3.4. Isotherm binding studies

The binding capacities for both the Fe3O4 and Fe2O3 with Cu2+ and Pb2+ are shown in
Table 1. The capacities in Table 1, for both the Cu2+ and Pb2+ ions are for 1 h of contact
with each of the respective nanomaterials at the optimum binding pH. The binding of both
Cu2+ and Pb2+ to the Fe3O4 and Fe2O3 nanomaterials was found to follow the Langmuir
Isotherm model. The isotherm data were plotted were fitted using the Langmuir Isotherm
equation in linear form, which resulted in linear plots with R2 values of 0.99 or better. The
linear form of the Langmuir equation is shown below:
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Where qe is the equilibrium concentration of the metal (copper or lead), Qo is the binding
capacity of the nanomaterial (Fe3O4 or Fe2O3), b is a constant, and Ce is the initial metal
concentration. By plotting 1/qe vs 1/Ce and employing the linearized Langmuir equation the
intercept of the line can be used to calculate the binding capacity of the adsorbent. The

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Langmuir adsorption model for lead removal using Fe3O4 was also observed in a study
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conducted by (5). Studies conducted using amino functionalized Fe3O4 (30), biomass coated
Fe3O4 (31) and γ-AlOOH @ SiO2/Fe3O4 (32) similarly, observed Langmuir adsorption for
both copper and lead. In the present study the binding of copper and lead to both the Fe3O4
and Fe2O3 was found to be fitted best using the Langmuir adsorption model. The Langmuir
adsorption model suggests single layer of metal ions adsorbing to the surface of the
nanomaterial.

Table 1 shows that both copper and lead have high binding capacity for both of the
adsorbents tested. Lead was determined to have a binding capacity of 166.67 mg/g for
Fe3O4 and 45.45 mg/g for Fe2O3. These results are significantly higher than Fe3O4 binding
capacities reported by others (8,19). Additional studies obtained Fe3O4 capacities only
slightly lower, 101.4 mg/g and 111.1 mg/g, than the capacities obtained in the present study
(10, 33). The results obtained for lead in this study were also compared binding capacities
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for lead binding to similar other metal oxides. Recillas et al., found high uptake of lead with
TiO2 was 159 mg/g and CeO2 bound 189 mg/g, Mahdavi et al., achieved 119.1 mg/g lead
binding with ZnO nanoparticles, but only 14.2 mg/g binding with CuO nanoparticles (8,10).
Further comparing the Fe3O4 nanoparticles synthesized in the present study showed higher
binding capacities than those observed in biosorbents such as sawdust, neem bark, and
macrophyte biosorbent materials (33, 35). Studies that utilized Fe3O4 functionalized with
various materials showed mixed results with binding capacities ranging from 64.50 mg/g to
598.8 mg/g (5, 33, 36). Using an Iron based material, Castaldi et al. showed that iron based
water treatment residuals had adsorption capacities of 0.194 and 0.106 mmol/g or 40.20 and
6.73 mg/g for Pb2+ and Cu2+ ions at pH 4.5 (37). In the same manuscript Castaldi et al.
showed that an Al based water treatment residual has capacities of 0.073 mmol/g and 0.065
mmol/g, or 15.2 and 4.13 mg/g, for Pb2+ and Cu2+, respectively (37).
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Binding capacities of 37.04 mg/g and 19.31 mg/g were observed for copper to Fe3O4 and
Fe2O3, respectively. Recent studies in the literature have shown variable results, ranging
from very low capacities of 6 mg/g to high capacities of 52 mg/g(10, 38–40). Higher copper
removal has been reported with the use of ZnO and CuO as well as Fe3O4 functionalized
with polymers and polymeric beads (10,31, 38–40). However, these binding capacities are
not specifically for the nanomaterial under investigation, but a combination of the
nanomaterial and the ligand used to functionalize the nanomaterial. The use of macrophyte
biomaterial obtained varying removal capacities ranging from 19.7 mg/g to 40.8 mg/g, with
the removal dependent on the species of macrophyte used in the study. The variation of
binding capacities observed for copper and lead to various materials suggest that binding
capacity is highly dependent on particle size and experimental conditions.
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3.5. Effects of coexisting cations

The effect of naturally occurring interfering cations ions Na+, K+, Ca2+, or Mg2+ on the
binding of copper and lead to Fe3O4 are shown in Fig. 5. As can be seen in Fig 5A–D the
presence of these metal ions had no significant effect on the binding of either copper or lead
to the Fe3O4 nanomaterial. However, a small decrease in copper binding was observed in the
presence of Mg2+ at 3000 ppm. A study conducted by Dong et al., found that no interference

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occurred with the binding of lead to hydroxyapatite coated Fe3O4 in the presence of the
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same ions (33). A second study showed that Ca2+ ions had no observable effect on the
binding of lead to Fe3O4 at a Ca2+ concentration of 100 ppm (19). It was also observed in
the study by Nassar et al. that the addition of Co2+, Ni+, and Cd2+ ions at 100 ppm had no
significant effect on the binding of lead to Fe3O4. Fig. 6 shows the effects of the same metal
ions on the binding of copper and lead to synthesized Fe2O3 nanomaterial. Fig. 6A and 6B
also show that both Na+ and K+ ions had no significant effect on the binding of copper to the
Fe2O3 nanomateiral. However, the Pb2+ binding to Fe2O3 was observed to decrease to
approximately 70% in the presence of Na+ at 0.3 ppm. The binding of the Pb2+ ions
increased continually after the initial decrease with increasing Na+ concentration, reaching
95% removed at a Na+ concentration of 3000 ppm. This initial binding decrease in the
presence of low concentrations of interfering ions has been observed by other authors. The
binding of Cu2+ (Fig. 6C) was found to decrease at high concentrations of Mg2+ ions,
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whereas lead binding is unaffected up to 3000 ppm. Copper binding decreased to 85%
removal at 0.3 ppm Ca2+ and 88.5% removal at 3 ppm Ca2+. After this initial decrease,
binding increased to greater than 95% removal at concentrations 30 ppm and above. Lead
binding decreased to 90% at 0.3 ppm Ca2+, then increased to complete removal at
concentrations of 3 ppm and above.

The effects of multiple coexisting alkali and alkali earth (Na+, K+, Ca2+, and Mg2+) are
presented in Fig. 7. Fig. 7A shows that the presence of all of the coexisting ions has little to
no effect on the binding of copper or lead to Fe3O4. Fig. 7B shows similarly that the
presence of these ions do not affect the binding of copper or lead to Fe2O3. The effects of
Na+, K+, Ca2+, or Mg2+ ions on the removal of lead were similarly observed using
biosorbents (41). Deng et al., found that the presences of these ion individually had little
effect on the removal of lead using Cladophora fascicularis green algae (41). Similar results
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were obtained for binding copper using the using Cladophora fascicularis algae biosorbent
(42). There appears to be an antagonistic effect between some of the cations in solution and
Pb2+ or Cu2+ especially at the low concentrations of both ions. However, the data indicates
that the Cu2+ and Pb2+ ions are preferentially bound from aqueous solution, due to the high
binding of Cu2+ and Pb2+ from solution in the presence of extremely high concentrations of
the interfering cations. The combined interference study the molar ratio of the ions to the
Cu2+ was 86147:1 and the Pb2+ was 282184:1. Even in these extremely high amounts of
cations present in solution the Cu2+ and Pb2+ binding was still above 90%, which indicates a
strong affinity of both the Cu2+ and Pb2+ ions to the nanomaterials.

4. Conclusion
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Optimal binding conditions for copper and lead to two synthesized nanomaterials, Fe3O4
and Fe2O3, were explored. Binding was found to be pH dependent, with pH 4 chosen as the
optimal binding pH. Copper and lead binding was also found to be time independent, with
high removal occurring within the first 5 min of contact with the Fe3O4 nanomaterial and
within the first 20 min of contact with Fe2O3 nanomaterial. Nanomaterial binding was tested
in the presence of competing alkali metals and alkaline earth metals for any possible
interference. The presence of Na+, K+, Mg2+, and Ca2+ ions showed no significant effect on
the binding of either Cu2+ or Pb2+ to either Fe3O4 or Fe2O3. The data indicates that nano-

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sized iron oxides can provide high removal of copper and lead without the need of additional
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modifications to the surface with organic ligands or chelating agents.

Acknowledgments
Authors would like to thank the NIH UTPA RISE program (Grant Number 1R25GM100866-01) and the HHMI
(grant number 52007568). The Authors acknowledge financial support from the Welch Foundation for supporting
the Department of Chemistry (Grant number GB-0017) and UTPA for sponsoring this research project.

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Highlights
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Non-stabilized iron oxide nanoparticles were synthesized from 12–20 nm in size

Effects of pH, time, and interfering ions were investigated for low level Cu2+ and
Pb2+ removal

Pb2+ had higher binding capacity to the Fe3O4 nanomaterial

Cu2+ had higher binding capacity and Fe2O3 nanomaterial

Both Cu2+ and Pb2+ binding followed the Langmuir isotherm model.
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Fig. 1.
A. Powder X-ray diffraction pattern of synthesized Fe3O4. B. Powder X-ray diffraction
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pattern of synthesized Fe2O3.

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Fig. 2.
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A. pH profile for the binding of copper and lead to Fe3O4, pH 2 to pH 6. B. pH profile for
the binding of copper and lead to Fe2O3, pH 2 to pH 6.

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Fig. 3.
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A. Effects of contact time on the binding of copper and lead to Fe3O4. B. Effects of contact
time on the binding of copper and lead to Fe2O3.

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 Tamez et al. Page 16
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Fig. 4.
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A. Binding affinity of copper or lead to Fe3O4 in the presence of increasing concentrations

of copper and lead. B. Binding affinity of copper or lead to Fe2O3 in the presence of
increasing concentrations of copper and lead.

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 Tamez et al. Page 17
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Fig. 5.
A. Interference study of copper and lead binding to Fe3O4 in the presence of increasing
concentrations of Na+ ions. B. Interference study of copper and lead binding to Fe3O4 in the
presence of increasing concentrations of K+ ions. C. Interference study of copper and lead
binding to Fe3O4 in the presence of increasing concentrations of Mg2+ ions. D. Interference
study of copper and lead binding to Fe3O4 in the presence of increasing concentrations of
Ca2+ ions.
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 Tamez et al. Page 18
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Fig. 6.
A. Interference study of copper and lead binding to Fe2O3 in the presence of increasing
concentrations of Na+ ions. B. Interference study of copper and lead binding to Fe2O3 in the
presence of increasing concentrations of K+ ions. C. Interference study of copper and lead
binding to Fe2O3 in the presence of increasing concentrations of Mg2+ ions. D. Interference
study of copper and lead binding to Fe2O3 in the presence of increasing concentrations of
Ca2+ ions.
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 Tamez et al. Page 19
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Fig. 7.
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A. Interference study of copper and lead binding to Fe3O4 in the presence of increasing
concentrations of Na+, K+, Mg2+, and Ca2+. B. Interference study of copper and lead
binding to Fe2O3 in the presence of increasing concentrations of Na+, K+, Mg2+, and Ca2+.

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Table 1

Binding capacities for copper and lead to Fe3O4 and Fe2O3 after 1 h of contact time at room temperature.
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Fe3O4 Fe2O3

Copper 37.04 mg/g 0.59 mmol/g 19.61 mg/g 0.31 mmol/g

Lead 166.67 mg/g 0.80 mmol/g 47.62 mg/g 0.23 mmol/g
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