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PAPER www.rsc.org/jem | Journal of Environmental Monitoring

Performance of an electrochemical COD (chemical oxygen demand)

sensor with an electrode-surface grinding unitw
Bong Geun Jeong,a Seok Min Yoon,a Chang Ho Choi,a Kil Koang Kwon,a
Moon Sik Hyun,b Dong Heui Yi,a Hyung Soo Park,b Mia Kimc and
Hyung Joo Kim*a
Received 31st August 2007, Accepted 9th October 2007
Published on 23 October 2007. Downloaded by University of Arizona on 30/05/2013 02:17:21.

First published as an Advance Article on the web 23rd October 2007

DOI: 10.1039/b713393f

An electrochemical COD (chemical oxygen demand) sensor using an electrode-surface grinding

unit was investigated. The electrolyzing (oxidizing) action of copper on an organic species was
used as the basis of the COD measuring sensor. Using a simple three-electrode cell and a surface
grinding unit, the organic species is activated by the catalytic action of copper and oxidized at a
working electrode, poised at a positive potential. When synthetic wastewater was fed into the
system, the measured Coulombic yields were found to be dependent on the COD of the synthetic
wastewater. A linear correlation between the Coulombic yields and the COD of the synthetic
wastewater was established (10–1000 mg L 1) when the electrode-surface grinding procedure was
activated briefly at 8 h intervals. When various kinds of wastewater samples obtained from
various sewage treatment plants were measured, linear correlations (r2 Z 0.92) between the
measured EOD (electrochemical oxygen demand) value and COD of the samples were observed.
At a practical wastewater treatment plant, the measurement system was successfully operated with
high accuracy and good stability over 3 months. These experimental results show that the
application of the measurement system would be a rapid and practical method for the
determination of COD in water industries.

Introduction entailed automated or simplified versions of conventional

Chemical oxygen demand (COD) refers to the oxygen required
for complete oxidation of organic species in a water sample.1,2
For the measurement of COD using an official (conventional)
method, the organic matter contained in a given sample of
water is oxidized by adding a known excess of a strong oxidant
(e.g. dichromate). After a refluxing digestion step, the COD
can be calculated by titrating the excess oxidant with Mohr’s
salt.3 In some countries, in spite of its lesser oxidation power
with poor reproducibility, permanganate is used as the oxidant
for the COD test because the dichromate is itself a heavy metal
pollutant.1,2 In addition, the conventional COD test procedure
using the chemical oxidants with the digestion step is time-
consuming, and it demands qualified personnel and expensive
and/or poisonous reagents.2,4 Thus, recently, several alterna-
tive methods, such as flow injection analysis, microwave
digestion, applications of permanganate ion-selective electro-
des and glass electrodes have been developed to overcome
some of these disadvantages.5–13 These methods, however,
a
Department of Microbial Engineering, Konkuk University,
Gwangjin-Gu, Seoul 143-701, Korea. E-mail:
hyungkim@konkuk.ac.kr; Fax: +82-2-446-2677;
Tel: +82-2-2049-6111
b
KORBI Co. Ltd, Doosan Venture Digm #826Dongan-Gu, Anyang-si,
Gyeonggi-do, 431-070, Korea
c
Korea BIO-IT Foundry Center@Busan, Pusan National University,
Geumjeong-gu, Busan, 609-735, Korea
w The HTML version of this article has been enhanced with colour
images.
methods, and there remains a continuing need for rapid,
simple and accurate COD test methods that will allow more
efficient on-line monitoring and control of wastewater
quality.14
The general requirements for rapid COD monitoring meth-
ods are as follows: (i) fast, accurate, and reliable results; (ii)
simple operation; (iii) low running cost; (iv) monitoring with
readily available, stable and safe reagents; (v) compatibility
with the conventional COD test results and computerized
data-handling systems; (vi) wide linear detection range; (vii)
‘‘operation and forget’’ capability (i.e. maintenance-free for
long-term operation, i.e. over 60 days at a practical loca-
tion).15,16 In attempts to satisfy these requirements, several
methods which are based on the photochemical reactions have
been developed, such as a photocatalytic sensor,1,4 ozonation
chemiluminescence,17 and flame atomic absorption spectro-
metry.3 Though these methods have the potential of applica-
tion to a high degree of automation and precision, the
instrumentation is costly, and requires careful, regular main-
tenance. Apart from the photochemical sensor, COD sensors
based on the electro-catalytic activity of anodic material
working electrode have been explored as a novel means of
COD measurement.2,7,18,19,20 Several anodic materials and
like-metals (e.g. Pt, Ag, Au, Cu, PtOx, PbO2 etc.) have
demonstrated good surface catalytic activity to oxidize differ-
ent organic compounds.21,22 For example, the use of copper as
an electro-catalyst for the alkaline oxidation of organic s
pecies, such as carbohydrates and amino acids, which are

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Table 1 General characteristics (average values) of the samples from the five different sewage treatment plants in each day (samples were collected
from 16 Feb 2006 to 25 Feb 2006, DO: dissolved oxygen, SS: suspended solid)
Nanji Anyang
(16 Feb 2006) (17 Feb 2006)
Temp/1C 12.1 10.8
pH 7.1 7.3
DO/mg L 1 0.7 0.5
1
COD/mg L 22.2 67.8
SS/mg L 1 39 77.2
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thought to be mainly responsible for the COD, has been
described.18 It was demonstrated that the catalytic activity of
copper was able to promote the oxidation of organic matter at
the electrode surface to water and carbon dioxide. Previous
research clearly showed that the electrons released during
oxidation can be measured as an electrical current, which is
proportional to the COD value of the solution being ana-
lyzed.18,21,22,23 The electrochemical oxidation mechanisms of
organic matter and the stoichiometric concept of the oxidation
were also proposed.21,22 Frequently, the term ‘electrochemical
oxygen demand’ (EOD), instead of COD, is used for these
electrochemical methods, which is defined as the oxygen
equivalent of the charge consumed during electrochemical
oxidation of the organic species of a sample.21,22,23 As both
parameters express the concentration of total organic matter
in solution, the only difference between EOD and COD is the
oxidation method of these organic species.14 However, it
should be noted that a major drawback associated with the
electrochemical method using a metal electrode is the contam-
ination and/or the accumulation of inactive metal oxidant at
the surface of the electrode in the form of residues left after
reaction. In continuous operation at a practical site, the
inactivation of metal electrodes by contamination presents a
major problem, and may lead to inaccurate data.23,24
In the authors’ previous work,24 a COD sensor using a
copper working electrode and an electrode-surface grinding
unit was examined, and it was found that the method can be
used successfully for COD measurement for a limited opera-
tion time (i.e. up to 24 h of measurement). The experiments
focused on establishing the basic experimental conditions for
the electrochemical COD measurement using glucose solutions
and real wastewater from a plant as laboratory samples.24
The present study describes demonstrations of a COD
sensor system capable of on-line, near real-time monitoring
of COD for real wastewater treatment, and is divided into two
parts. Firstly, using wastewaters obtained from sewage treat-
ment plants, the COD measurement capability of the system
was demonstrated. Secondly, at a wastewater treatment plant
using the real wastewater, the sensor system was examined for
field applicability, reproducibility and operational durability.
Materials and methods
Wastewater samples
For the estimation of the detection range of the COD sensor,
glucose solution was used as synthetic wastewater. The COD
concentration (generally 10 to 2000 mg L 1) of the synthetic
wastewater was maintained by additions of the appropriate
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Jungnang Konkuk Univ. Tancheon
(20 Feb 2006) (21 Feb 2006) (25 Feb 2006)
11.3 9.9 8.4
7.0 7.2 7.6
0.7 0.9 1.2
35.1 8.1 21.7
61.8 15.2 37.5
amounts of glucose to distilled water. The COD of the
solutions were measured by the conventional COD test meth-
od.25 The synthetic wastewater was then autoclaved at 121 1C
for 15 min to prevent the action of the microorganisms and
stored at 4 1C before use.4 In the case of real wastewater,
samples were obtained from five different sewage treatment
plants in Korea (Nanji, Anyang, Jungnang, Tancheon, and
Konkuk University sewage treatment plants) from 16 Feb to
25 Feb 2006. All samples were collected at a depth of 50 cm at
the first sedimentation tank at 9:00 am, 11:00 am, 13:00 pm,
15:00 pm and were kept below 4 1C. The general character-
istics of the samples (at the first sedimentation tank) are
described in Table 1. Conventional COD determinations on
the collected samples were pre-established using the official
test method.25 All experiments were carried out within 12 h
after sample collection.
Electrodes and electrochemical cell
A COD sensor with a three-electrode electrochemical cell
configuration (working volume: 3 mL) and the electrode-
surface grinding unit was prepared (Fig. 1). A copper tube
(99.99%, 30 mm outside diameter, 20 mm thickness, 10 mm
length, 463 mm2 surface area, Poongsan Metal, Korea), a
stainless steel cylinder (40 mm outside diameter, 3 mm thick-
ness, 348 mm2 surface area, stainless steel 316 L, Yonnam
Metal, Korea), and an Ag/AgCl electrode (Model No.
2731401-35-S8, Phoenix, USA) were used, respectively, as
working electrode, counter electrode and reference electrode.
Using a compressed diamond grinding block (3  3  30 mm,
DIA grinding stone, Dawoori, Korea) mounted on a servo-
motor unit (HS-85MG, Hitec RCD, Korea), the electrode-
surface grinding action was achieved by rotation of the grind-
ing block. A small stick of acrylic stick was fitted with the
working electrode surface for the preparation of a grinding
block rest. Generally, the grinding operation was performed
for 30 s (10 times, forward and backward, over a 901 arc) every
8 h and the pressure of the working electrode upon the
diamond grinding block was maintained using a coiled spring.
After the grinding action, the grinding block was set at the
acrylic non-conductive block rest to prevent formation of
electrochemical noise and the measurement was performed.
The procedures ensured that a relatively clean electrode sur-
face was exposed to the solution under test, thus avoiding
significant effects arising from surface adsorption of organic
oxidation products.
Configuration and operation of the system
The schematics of the COD monitoring system, including the
COD sensor and the grinding unit, are represented in Fig. 2.
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Fig. 1 Schematic representation (A) and photo (B) of the electrochemical cell. During the measurement operation, the grinding block was set at
the non-conductive block rest (an acrylic block).
For the system operation, 1 : 1 (v : v) of wastewater sample :
electrolyte (0.1 M NaOH) mixture was added to the sensor
(flow rate: 1 mL min 1) using a programmable multi-channel
peristaltic pump (ISM597A, Ismatec, Switzerland). To distin-
guish the oxidation current of the organic matters from back-
Fig. 2 Schematic representation of the COD measurement system.
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ground current, the same volume of distilled water was fed to
the sensor at intervals of 300 s, instead of wastewater sample.
DC amperometry was used for electrochemical COD measure-
ment of the wastewater samples.20,22–24,26 Oxidation of organic
matter by the copper as an electro-catalyst was achieved using
a potentiostat (WMPG 1000, IBM PC controlled, Wonatech
Co. Korea), at a constant potential of 600 mV versus Ag/AgCl
(i.e. below 700–800 mV, which is usually regarded as the onset
potential of water oxidation).24 This process had a constant
temperature (30 1C). For the precise control of the temperature
sensor unit, a temperature control system using a thermo-electric
chip module (SKT, Korea) was used. The data was recorded
using a personal computer with the exclusive software of WMPG.
This software was used to calculate the Coulombic yield (current
(I)  time (t)) produced from the COD sensor. The measured
data were given as an on-line graphic display, which showed
values at 1 min intervals or as required. The data (i.e. Coulombic
yield) from the sensor were calculated as EOD, estimated from a
pre-established calibration curve (COD vs. Coulombic yield).
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Table 2 General characteristics of the samples collected from the
Jungnang sewage treatment plant during 3 months (18 Feb 2006–
18 May 2006, DO: dissolved oxygen, SS: suspended solid)
Parameter Average Range
Temp/1C 15.7 8.3–22.6
pH 7.4 7.0–7.7
DO/mg L 1 1.4 0.3–2.8
COD/mg L 1 45.2 25.4–91.2
SS/mg L 1 87 21–245
Total nitrogen/mg L 1 18.4 7.2–25.8
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1
Total phosphorous/mg L 2.1 1.1–4.9
Field application site
The application site was located in Jungnang sewage treatment
plant (Seoul, Korea). The COD monitoring system was in-
stalled at the first sedimentation tank in the plant. The inflow
to the system was taken from the wastewater from the tank.
The general characteristics of the inflow sample (at the first
sedimentation tank) are described in Table 2. The temperature
was varied from 8.3 to 22.6 1C (average: 15.7 1C). The COD
was varied from 25.4 to 91.2 mg L 1 (average: 45.2 mg L 1).
In the case of field application, a particle remover for the
wastewater was also used to prevent clogging of the system.27
Results and discussion
Estimation of the detection range of the COD sensor
Typical traces of the current change due to the oxidation of
organic matter at the surface of the electrode with different
concentrations of COD (synthetic wastewater) are shown in
Fig. 3. The general form of DC amperometric response to the
addition of the synthetic wastewater–NaOH mixture (COD
load), was a rise in current as a function of time, decaying
when the NaOH–distilled water solution was fed to the cell, so
removing the organic matter. The measured Coulombic yields
varied with the concentrations of COD of wastewater fed to
the sensor. Using various concentrations of the synthetic
wastewater, the detection range of the sensor was established.
Measurement of the current change after successive additions
Fig. 3 Electrochemical signal generation patterns from the electro-
chemical cell with different concentrations of synthetic wastewater.
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of a known concentration of COD (synthetic wastewater) to
the sensor showed an increase Coulombic yield with increasing
COD concentration (Fig. 4A). When the grinding unit was
operated, no significant signal was observed, apart from a
minor perturbation at the initial stage of grinding. When the
grinding unit was not operated, however, a decrease in current
was observed under the same concentration of COD (Fig. 4B).
Fig. 4C shows the correlation between Coulombic yield and
the different concentrations of COD fed over the range of 10
to 2000 mg L 1, with and without the grinding. In the case of
grinding, a clear linear relationship was obtained between the
range of 10 to 1000 mg L 1 (line (b): correlation coefficient;
r2 = 0.98). However, over 1000 mg L 1, the Coulombic yield
reached a plateau with the COD increase (Fig. 4C, line (a))
The plateau at the high concentration of COD range was
probably due to the saturation of organic matter at the limited
surface area of the electrode28 or was probably due to the
presence of other effects, such as corrosion or deactivation or
polymerfilm formation.29 In the case of the COD measure-
ment without the grinding, a relatively low correlation (r2 = 0.781)
between the COD of wastewaters and Coulombic yield was
observed (Fig. 4C, line (c)) compared to the measurement with
the grinding, probably because of attachment of oxidant residue
and/or accumulation of inactive metal oxidant at the surface of the
electrode. From these results, it can be deduced that the Coulombic
yields (i.e. EOD) from the sensor, when the electrode-surface
grinding procedure was in operation, could be conveniently con-
verted into COD values for a limited measurement range.
Electrochemical COD measurement with various real
wastewater samples
Using various real wastewater samples obtained from five
sewage treatment plants, the reproducibility and accuracy of
the COD sensor system for real wastewater samples were
examined. To obtain different COD concentrations of waste-
water, samples were collected at 9:00 am, 11:00 am, 13:00 pm,
and 15:00 pm in the day from each sewage treatment plant.
The grinding of the electrode surface was set at once every 8 h
for a period of 30 s. Fig. 5 shows the results of electrochemical
measurement of organic matter using different concentrations
of COD. In general, all the wastewaters used in this study, at
different kinds of organic matter with different concentrations,
generated an oxidation current, and the current generation
pattern was closely related to the conventional COD value.
When the correlation between the produced EOD data and the
conventional COD value were compared, reasonable correla-
tions (correlation coefficient, r2, ranged from 0.92 to 0.95) were
obtained. These results indicate that the COD sensor system
can be applied to advantage in practical sewage treatment
plants. The differences of EOD obtained for the various waste-
water samples, however, may be due to differences of waste-
water characteristics of each plant. Therefore, for a precise
measurement of COD using the system, a pre-calibration
between EOD and conventional COD would be required.1–3,24
Long term application of the COD monitoring system at a
sewage treatment plant
To examine the on-line capability and durability of the system,
the COD sensor system was installed at the wastewater
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Fig. 4 Signal generations from the electrochemical cell with different
concentrations of synthetic wastewater (A: using grinding unit, arrows
indicate grinding points, B: without grinding unit) and correlation
curves (C) between the conventional COD and the Coulombic yield
with different COD concentrations (a): using grinding unit, (b): ideal
correlation, (c): without grinding unit.
treatment plant. A particle remover was also installed to
prevent clogging of the sensor. Over 90 days, the measurement
system was successfully operated without any serious pro-
blems. Fig. 6 illustrates COD measurement data using the
sensor system (Fig. 6A) and the current-generation pattern
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Fig. 5 Electrochemical measurement of COD with various practical
wastewaters (see the text for details).
from the system (Fig. 6B) for 90 days at the plant. The
conventional COD profile during the 90 days is also shown
in Fig. 6A. As shown in Fig. 5, the EOD pattern in this
experiment (Fig. 6) varied with the variation in COD concen-
tration of the real wastewater. When the Coulombic yield (i.e.
EOD) from the system was compared with the conventional
COD measurement results, a clear linear relationship (correla-
tion coefficient; r2 = 0.98) was observed (Fig. 6C). During the
experimental period, there were several hours of interruption
due to the sudden power failure and the exchange of the
reference electrode. However, when the experimental condi-
tions were recovered, no significant variation in COD
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Fig. 6 Application of the COD monitoring system to the Jungnang
sewage treatment plant (Seoul, Korea) for 3 months (18 Feb 2006–
18 May 2006). (A) EOD profile and conventional COD (J: conven-
tional COD concentration measured by standard method); (B) current
generation pattern from the system; (C) correlation curve between the
conventional COD concentration and Coulombic yield from the
system.
measurement performance was observed. These experimental
results show that the real-time, on-line monitoring of COD at
a practical sewage treatment plant could be possible using a
simple copper electrode and surface grinding unit. It should be
noted that the durability of the sensor over three months was
achieved using the grinding unit. About 1 mm thickness of the
rotating working electrode compartment was worn during the
operation. According to previous research, major important
drawbacks of the electrochemical sensor for wastewater mon-
itoring, especially for long-term operation, are the contamina-
tion of the electrode surface by oxide film formation and
residual organic matter.23,24,29,30 Several attempts have been
made to regenerate the electrode by electrochemical, physical,
and chemical methods.31 These approaches, however, have
solved only some of the problems associated with electroche-
mical methods, and there remains a continuing need for
convenient, accurate, and economic COD measurement meth-
ods that will allow more efficient monitoring and control of
COD of wastewater. Because previous regeneration methods
have generally involved sophisticated devices, such as a spe-
cific operation program with electrochemical devices, a water
jet, or an ultrasonic sonicator, the operation procedures
require careful and periodic maintenance. In the present
studies, however, the attachment of a simple rotating grinder
onto the electrode surface facilitates the continuous applica-
tion of the metal electrode. Pre-calibration is an important
parameter for the operation of the system, especially in the
practical field application. Other factors that influence the
monitoring performance include the surface area of the
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electrode, the grinding time, the frequency of the grinding
procedure, and the life span of the reference and counter
electrodes. Precautions to clogging of flow should also be
considered in order to achieve reliable application of the
COD sensor system. Further work is now required to develop
a more reliable sensor, to increase the operation period, and to
explore further applications of the COD monitoring system.
Acknowledgements
This subject is supported by Korean Ministry of Environment
(The Eco-Technopia 21 project, 2005).
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