A Comparative Electrochemical Study On Arsenic Removal Using Iron, Aluminum

A Comparative Electrochemical Study on Arsenic Removal Using Iron, Aluminum,
and Copper Electrodes

Jewel Andrew Gomes
1
, Md. Sanoar Rahman
2
, Kamol Das
2
, Srikanth Varma
2
, David L.
Cocke
3

1
Department of Chemical Engineering
2
Department of Civil Engineering
3
Gill Chair of Chemical Engineering
Lamar University, Beaumont, TX 77710

Arsenic is considered as one of the toxic materials being controlled
by environmental protection agencies in several developed and
developing countries. It is found in the nature as constituents of the
soil, minerals and also in various organic forms. It enters the air,
water, and land from wind-blown dust and gets into water from
runoff, leaching, soil erosion and anthropogenically from
chemicals used for wood preservation, insecticides, medicine,
military purpose, pigments, and electronic circuitries. There are
several techniques available for removal of arsenic, such as
coagulation/filtration, lime softening, ion exchange, reverse
osmosis, nanofiltration, wet chemical, and electrochemical.
Electrocoagulation has been found as one of the most efficient
techniques to remove inorganic arsenic with more than 99%
efficiency. In this paper, we present our work on electrochemical
treatment of both the inorganic and organic arsenic from water
using various sacrificial electrode materials, i.e., iron, aluminum,
copper, and combination of them. The floc produced by this
method has been also characterized using XRD, SEM/EDS, and
cyclic voltammetry.

Introduction
Arsenic, a toxic trace element present in natural waters has become a major unavoidable
threat for the life of human beings and useful microorganisms. Arsenic concentration in
soils and water can become elevated due to several reasons like, mineral dissolution, use
of arsenical pesticides, disposal of fly ash, mine drainage, and geothermal discharge [1].
It is present in natural waters in both inorganic and organic forms. The most common
form of inorganic arsenic in surface water is arsenate (As(V)), while under highly
reducing conditions, such as anaerobic ground waters, arsenic may form reduced arsenite
(As(III)) forms [2]. The toxicity of As(III) is much higher than that of As(V). Arsenic
concentration in soils and water can become elevated due to several reasons like, mineral
dissolution, use of arsenical pesticides, disposal of fly ash, mine drainage, and geothermal
discharge [1]. The concentration of arsenic species is mainly dependent on redox
potentials [3] and pH [4]. Arsenate species are the only species that can exist at high
redox potentials on the entire pH range. Electrocoagulation (EC) is a simple, efficient and
promising method where the flocculating agent is generated by electrooxidation of a
ECS Transactions, 25 (28) 59-68 (2010)
10.1149/1.3309678 The Electrochemical Society
59
Downloaded 07 Sep 2010 to 133.87.247.206. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp
sacrificial anode. In this process, treatment is done without adding any chemical
coagulant or flocculants, thus reducing the amount of sludge that must be disposed [5]. In
an EC process, the coagulating ions are produced in situ involving three successive
stages: (i) formation of coagulants by electrolytic oxidation of the sacrificial electrode,
such as copper, iron or aluminum, (ii) destabilization of the contaminants, particulate
suspension and breaking of emulsions, (iii) aggregation of the destabilized phases to form
flocs. Cu/Fe/Al get dissolved from the anode generating corresponding metal ions, which
almost immediately hydrolyze to polymeric copper, iron or aluminum oxyhydroxides.
These polymeric oxyhydroxides are excellent coagulating agents. Figure 1 shows a
conceptual sketch of the electrocoagulation mechanism. As shown in the Figure 1, the
anodic reaction involves the dissolution of metal, and the cathodic reaction involves the
formation of hydrogen gas and hydroxide ions [1].The sacrificial metal anodes are used
to continuously produce polymeric oxyhydroxides in the vicinity of the anode.
Coagulation occurs when these metal cations combine with the negative particles carried
towards the anode by electrophoretic motion. Contaminants present in the wastewater
stream are treated either by chemical reactions and precipitation or physical and chemical
attachment to colloidal materials being generated by the electrode erosion. They are then
removed by electroflotation, or sedimentation and filtration. Thus, rather than adding
coagulating chemicals as in conventional coagulation process, these coagulating agents
are generated in situ [6].

Figure 1. Conceptual sketch of the electrocoagulation mechanism. M and X indicate
electrodes. They may be different or same materials. n indicates charge of the metallic
ions produced. The arrows indicate the migration of electrolysis gases towards top of the
solution.
60
Experimental

The electrodes used in this study consisted of copper, aluminum and iron plates. Stock
inorganic arsenic solutions were prepared according to the EPA standard method by
dissolving arsenic oxide (As
2
O
3
) in 20% (w/v) potassium hydroxide and then diluting to
with DI water. Solutions of lower concentrations were prepared by proper dilution. For
the organic arsenic, the solution was prepared by dissolving dimethylarsinic acid
(DMA/cacodylic acid) [(CH
3
)
2
As(O)OH] to DI water. Solutions of lower concentration
were prepared by proper dilution of the sample. The pH of the solution was adjusted by
adding either 3 M sodium hydroxide or sulfuric acid. Electrocoagulation was conducted
at different pH using three combinations of electrodes (CuCu, CuFe, and CuAl). The
polarity of the electrodes were reversed every 15 min. The solution was constantly stirred
using a magnetic stirrer to reduce the mass transport over potential of the EC cell [6]. The
treated organic sample was prepared for measurement following EPA method (acid
digestion). The sample was digested with nitric acid and hydrogen peroxide then
analyzed for total arsenic in the solution.

Electrocoagulation procedure

EC was run both in flow-through EC apparatus (FTEA, manufacturer: Kaselco) and
beaker-size reactor. The FTEA essentially consists of a flow-through cell, the electrode
assembly, the feed pump and the DC power supply unit. A schematic diagram of the
FTEA is shown in Figure 2. The volume of the reactor was 450 mL. The beaker size EC
was carried out in a 250 ml beaker with magnetic stirrer, using vertically positioned
electrodes dipped in the wastewater. The current and voltage during the EC process were
checked using Cen-Tech multimeters. The current density was 30 mA/cm
2
and 8.3
mA/cm
2
for the beaker-size reactor and FTEA reactor, respectively. The pH of the
solutions before and after EC was measured by an Oakton pH meter. EC was run for a
certain period of time. After that, the EC-mixture was filtered and the precipitate was
dried. The solid precipitate was characterized by XRD, SEM/EDS, FTIR and Cyclic
voltammetry. The filtrate was used for determining the amount of residual arsenic.

61

Figure 2. Schematic diagram of Kaselco bench reactor

Results and discussion

Arsenic removal

The Nanoband explorer (Trace Detect) was used to measure arsenic concentrations and
filtrate solutions after EC process showed that more than 99.9% of arsenic was removed
by using CuCu electrode pair in the treatment of inorganic arsenic. The removal
efficiency varied from 86.1% to more than 99.9% (see Table I). CuCu or combination of
Cu-Fe plates as sacrificial electrodes in EC process is very promising for arsenic removal
as it showed in the data. The initial pH 6 was found to be the optimum pH for maximum
arsenic removal. The rate of formation of metalarsenate/arsenite complexes may be
lower due to solubility effects than that at pH 6.

62
Table I. EC treatment of synthetic inorganic arsenic and their removal efficiencies

Material characterization

XRD characterization of electrode by-products

X-ray diffraction spectrum of different combinations electrodes by products was taken
and presented in Figure 3-5. X-ray diffraction analysis of CuCu electrode by-product
showed broad and shallow diffraction peaks. It showed (see Figure 3) presence of tenorite
(syn-CuO) which is monoclinic and cubic cuprite (syn- Cu
2
O). The XRD also showed
small peak at 12.7 (2 Scale) which may be of copper arsenic oxide [Cu
4
(AsO
4
)
2
O]. The
analysis of Cu Fe electrode by-product also showed the presence of tenorite (syn-CuO)
and cuprite (syn- Cu
2
O) (see Figure 4). It also showed presence of magnetite (Fe
3
O
4
) and
sympesite at 11.1 (2 Scale), 13.16 (2 Scale) and 23.05 (2 Scale). In the Cu-Al
electrode by product analysis, it also showed tenorite (syn-CuO) and cuprite (syn- Cu
2
O).
Other than that there was also presence of orthorhombic diaspore [AlO(OH)] and
monoclinic structured bayerite [Al(OH)
3
].

Reactor
Type
Electrode pH

pH (After
treatment)
As
(ppm)
(Initial)
As
(ppm)
(Final)
Removal
Efficiency
(%)
Current
Density
(mA/cm2)
FTEA,
Cu, 2 EC
Cu 4.0 11.6 50.000 0.300 99.4 8.3
Beaker Cu-Cu 4.0 8.1 1.000 0.005 99.5 30.0
6.0 7.9 1.000 <0.001 >99.9 30.0
Beaker Cu-Fe 4.0 9.8 1.000 0.009 91.1 30.0
6.0 7.8 1.000 0.004 99.6 30.0
Beaker Cu-Al 4.0 9.7 1.000 0.139 86.1 30.0
6.0 9.5 1.000 0.025 97.5 30.0
63

Figure 3. X-ray diffraction analysis of CuCu electrode by-product. The x-axis indicates
2-theta (ranging from 2 to 70 degrees) and the y-axis linear intensity in counts (ranging
from 6 to 1000). The red line diffraction pattern indicates tenorite, and the blue line
cuprite.

Figure 4. X-ray diffraction analysis of CuFe electrode by-product. The x-axis indicates
from 0 to 550). The red line diffraction pattern indicates tenorite, the blue line cuprite,
and the pink line magnetite.
2-Theta Scale
2-Theta Scale
64

Figure 5. X-ray diffraction analysis of CuAl electrode by-product. The x-axis indicates
from 6 to 500). The blue line diffraction pattern indicates tenorite, the red line cuprite, the
green line diaspore, and the pink line bayerite..

SEM and XRF

SEM and XRF were also performed on the EC by products. The SEM in general showed
amorphocity and crystallinity of different sizes in the by products from EC. Figure 6
shows examplary the SEM image of EC by products. The elemental analysis by XRF
confirmed the presence of As removed from the sample solution. Other elements detected
in the floc come from the adsorption of the conducting electrolytes, chemicals used in the
experiments and the scrap impurities of the Cu, Al and Fe electrodes.

2-Theta Scale
65

Figure 6. SEM image of the EC-byproducts containing initial As of 1 ppm at initial pH of
6 with the CuFe electrode system.

Cyclic Voltammetry

Electrochemical analysis of EC byproducts were studied using cyclic voltammetry
technique with Voltalab 10 instrument. The voltammogram of EC by product shows
cathodic (reduction) peaks at -375 mV vs SSCE (saturated silver/silver chloride
electrode) and around -10mV vs SSCE. The conditions of the experiment are as follows:
scan rate- 5 mV/sec, electrolyte- phosphate buffer, pH- 9, reference electrode- SSSE, and
temperature- 25 C. These points observed may be due to reduction of Cu
2+
or Cu
+
at
those particular points. The proper identification is under progress.

66

Figure 7. Voltammogram of EC byproduct (Cu-Cu electrodes). The conditions of the
experiment: scan rate- 5 mV/sec, electrolyte- phosphate buffer, pH- 9, reference
electrode- saturated silver/silver chloride electrode, temperature: 25 C. The x-axis
indicates potential in mV (ranging from -600 mV to +600 mV) and y-axis indicates
current density in A/cm
2
(ranging from -10 to 80 A/cm
2
).

Conclusion

Electrocoagulation is effective in treatment of water contaminated with arsenic. In this
study we observed the efficiency of combinations of copper electrodes which works
better (in terms of removal efficiency) than aluminum and iron electrodes alone. The
frequent change of electrode-polarity may provide an efficient way for removal of both
organic and metallic pollutants from water. The elemental analysis by XRF and EDS
confirmed the presence of As removed from the sample solution. The XRD showed the
presence of tenorite (syn-CuO), cuprite (syn- Cu
2
O), magnetite (Fe
3
O
4
) and sympesite in
the EC by products. Other than that there was also presence of orthorhombic diaspore
[AlO(OH)] and monoclinic natured bayerite [Al(OH)
3
].

67

Acknowledgements

We greatly acknowledge the financial support from the Welch Foundation (V-1103),
USDA (2006-38899-03586), and Lamar University Research Enhancement Grant 2009.

References

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3. J.G. Hering, P.Y. Chen, J.A. Wilkie, M. Elimelech, and S. Liang, J. Am. Water
Works Assoc., 88, 155 (1996).
4. P.H. Masscheleyn, R.D. Delaune, W.H. Patrick Jr., Environ.Sci. Technol., 25,
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68

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