Emerging Technologies

Received: 17 March 2009 Revised: 8 April 2009 Accepted: 14 April 2009 Published online in Wiley Interscience: 28 May 2009

(www.interscience.wiley.com) DOI 10.1002/jctb.2214

Contributions of electrochemical oxidation

to waste-water treatment: fundamentals
and review of applications
Ángela Anglada, Ane Urtiaga∗ and Inmaculada Ortiz

Abstract
OVERVIEW: This paper provides an overview of some fundamental aspects of electrochemical oxidation and gives updated
information on the application of this technology to waste-water treatment. In recent years, electrochemical oxidation has
gained increasing interest due to its outstanding technical characteristics for eliminating a wide variety of pollutants normally
present in waste-waters such as refractory organic matter, nitrogen species and microorganisms.

IMPACT: The strict disposal limits and health quality standards set by legislation may be met by applying electrochemical
oxidation. However, treatment costs have to be cut down before full-scale application of this technology. Deployment of
electrochemical oxidation in combination with other technologies and the use of renewable sources to power this process are
two steps in this direction.

APPLICATIONS: Effluents from landfill and a wide diversity of industrial effluents including the agro-industry, chemical, textile,
tannery and food industry, have been effectively treated by this technology. Its high efficiency together with its disinfection
capabilities makes electro-oxidation a suitable technology for water reuse programs.

c 2009 Society of Chemical Industry

Keywords: electrochemical oxidation; waste-water treatment; process development; advanced oxidation processes

NOTATION line of investigation due to the high energy requirement of

Q = specific electrical charge (kAh m−3 ) electro-oxidation. As electricity is basically the only consumable in
W = specific energy consumption (kWh m−3 ) electrochemical oxidation, the use of photovoltaic (PV) modules as
I = current intensity (A) a power supply is also envisaged as a possible means of reducing
J = current density (A m−2 ) the operating costs,1 providing a sustainable solution. This paper
V = cell potential (V) considers the fundamentals of electrochemical oxidation and gives
A = electrode area (m2 ) a short overview on the potential applications of this technology
F = Faraday constant (96 487 C mol−1 ) in waste-water treatment. Special emphasis is put on the latest
v = volume of electrolyte (L) developments and some of the challenges that have yet to be
n = number of exchanged electrons (mole− mol−1 faced are highlighted.
pollutant)
[P]t = concentration of pollutant (mol L−1 ) at time t
[P]t+
t = concentration of pollutant (mol L−1 ) at time t +
t ELECTROCHEMICAL OXIDATION OF WASTE-
t = time (s) WATERS
Figure 1 shows a conceptual diagram of an electrochemical reactor
INTRODUCTION for waste-water electro-oxidation,2 which includes a power supply,
In recent years, the appearance of pollutants that are recalcitrant a cathode, an anode and the electrolyte.
to conventional biological and chemical treatments together with Electrochemical oxidation of pollutants can take place through
the stricter restrictions imposed by new legislation have caused two different oxidation mechanisms as shown in Fig. 2: (1) direct
much research work to focus on waste-water treatment by electro- anodic oxidation, where the pollutants are destroyed at the anode
oxidation processes. Electrochemical oxidation has been found to
be an environmentally benign technology able to mineralize
∗
completely non-biodegradable organic matter and to eliminate Correspondence to: Ane Urtiaga, Department of Chemical Engineering,
nitrogen species. Two lines of investigation have been followed: University of Cantabria, Avenida de los Castros s/n, 39005 Santander, Spain.
E-mail: [email protected]
(1) replacement of conventional processes by electrochemical
oxidation and (2) integration of electrochemical oxidation into
1747

Department of Chemical Engineering, University of Cantabria, Avenida de los

a treatment plant. Current research is focusing on the second Castros s/n, 39005 Santander, Spain

J Chem Technol Biotechnol 2009; 84: 1747–1755 www.soci.org

c 2009 Society of Chemical Industry
 www.soci.org Á Anglada, A Urtiaga, I Ortiz

Current supply Indirect oxidation

During indirect electrochemical oxidation, a strong oxidizing agent
+ - is electro-generated at the anode surface and then destroys the
pollutants in the bulk solution. The most common electrochemical
e- e-
oxidant is probably chlorine which is formed by the oxidation of
chloride at the anode. Although the role of active chlorine in the
oxidation of organic pollutants is not clear, ammonia oxidation is
usually acknowledged to take place through this mechanism.5,6
Anions The extensive use of active chlorine is due to the ubiquitous
presence of chloride in waste-waters and to its quite effective
Cations action. Other common oxidants that can be electrochemically
produced are hydrogen peroxide, peroxodisulfuric acid (H2 S2 O8 )
and ozone. Metal catalytic mediators (Ag+2 , Co+3 , Fe+3 , etc.) are
Anode Cathode
also employed for the generation of hydroxyl radicals, as occurs in
Oxidation Reduction
the electro-Fenton scheme. However, the use of metal ions may
processes processes
result in an effluent with a higher toxicity than that of the initial
Figure 1. Conceptual diagram of an electrochemical reactor. effluent. Thus, this approach requires a separation step to recover
the metallic species.7
surface; (2) indirect oxidation where a mediator (HClO, H2 S2 O8 and
others) is electrochemically generated to carry out the oxidation.
DESIGN OF AN ELECTROCHEMICAL OXIDATION
It has to be kept in mind that during electro-oxidation of aqueous
effluents, both oxidation mechanisms may coexist.3 PROCESS
In order to design an electrochemical oxidation system, the
electrode material, the configuration of the cell and the operating
Direct oxidation
conditions have to be taken into account.
Direct oxidation of pollutants takes place in two steps: (1) diffusion
of pollutants from the bulk solution to the anode surface and
(2) oxidation of pollutants at the anode surface. Consequently, Electrode material
the efficiency of the electrochemical process will depend on The choice of electrode material is of paramount importance as
the relationship between mass transfer of the substrate and it affects the selectivity and the efficiency of the process. The
electron transfer at the electrode surface. The rate of electron electrode material must have the following properties:
transfer is determined by the electrode activity and current
• High physical and chemical stability; resistance to erosion,
density.
corrosion and formation of passivation layers.
During anodic oxidation of organic pollutants, two different
• High electrical conductivity.
pathways can be followed:4
• Catalytic activity and selectivity.
• Electrochemical conversion. Organic compounds are only • Low cost/life ratio. The use of electrode materials that are
partially oxidized (Equation (1)). Therefore, a subsequent inexpensive and durable must be favoured.
treatment may be required.
In order to assess the selectivity of an anode material, competition
R −−−→ RO + e −
(1) between the oxidation of organics at the anode and the side
reaction of oxygen evolution must be considered:
• Electrochemical combustion. Organic compounds are trans-
formed into water, carbon dioxide and other inorganic 2H2 O −−−→ O2 + 4H+ + 4e− (3)
components:
The oxidation of water to oxygen occurs at approximately 1.2 V
R −−−→ CO2 + H2 O + Salts + e− (2) vs. NHE (normal hydrogen electrode). However, in fact, a higher

(a) (b)
Pollutants Mediator Pollutants

e- e- Oxidation
in the bulk

Destroyed Oxidant Destroyed

pollutants pollutants
Anode Anode
Electrolyte Electrolyte
surface surface
DIRECT OXIDATION INDIRECT OXIDATION
1748

Figure 2. Schemes for (a) direct and (b) indirect electrolytic treatment of pollutants.

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c 2009 Society of Chemical Industry J Chem Technol Biotechnol 2009; 84: 1747–1755
Contributions of electrochemical oxidation to waste-water treatment www.soci.org

Cell configuration
Table 1. Potential of oxygen evolution of different anodes, V versus
NHE8 One of the most important issues in cell design is to maintain
high mass transfer rates as the main reactions that take place
Anode Potential (V) Conditions in electrochemical oxidation processes take place on electrode
Pt 1.3 0.5 mol L−1 H2 SO4
surfaces. To improve mass transfer to the surface of the electrode,
Pt 1.6 0.5 mol L−1 H2 SO4
common methods such as gas sparging, high fluid velocity, use of
IrO2 1.6 0.5 mol L−1 H2 SO4 baffles and incorporation of various types of turbulence promoters
Graphite 1.7 0.5 mol L−1 H2 SO4 are employed. Sono-electrochemical processes have also been
PbO2 1.9 1 mol L−1 H2 SO4 tested to enhance mass transfer.8 Besides procuring a high mass
SnO2 1.9 0.5 mol L−1 H2 SO4 transfer rate, cell construction should account for easy access to
TiO2 2.2 1 mol L−1 H2 SO4 and exchange of cell components.11 In Fig. 3, an overview of the
Si/BDD 2.3 0.5 mol L−1 H2 SO4 various aspects that have to be considered in the design of an
Ti/BDD 2.7 0.5 mol L−1 H2 SO4 electrochemical reactor is shown.12
Two types of electrodes, mainly of two-dimensional and three-
dimensional construction exist. The latter guarantee a high value
of electrode surface to cell volume ratio. As can be seen in
voltage has to be applied for electrochemical oxidation of water Fig. 3, both types of electrodes can be classified into static
to occur at the anode. The difference between the value of the and moving electrodes. The use of moving electrodes leads
voltage at which the oxidation of water actually begins to take to increased values of the mass-transport coefficient due to
place, and the thermodynamic value is the oxygen evolution turbulence promotion. Among the two-dimensional electrodes,
overpotential.8 In Table 1, the oxygen evolution overpotential of static parallel and cylindrical electrode cells are used in the major
several electrode materials is presented. reactor designs in current studies of electrochemical oxidation of
Low O2 overvoltage anodes are characterized by a high elec- waste-waters. Cell designs using the parallel plate geometry in a
trochemical activity toward oxygen evolution and low chemical filter press arrangement are widely deployed due to the ease of
reactivity toward oxidation of organics. Effective oxidation of pol- scale-up to a larger electrode size, with more electrode pairs or an
lutants at these anodes may occur at low current densities; at high increased number of cell stacks.13
current densities, significant decrease of the current efficiency is Besides the electrode geometry and configuration, the configu-
expected due to the production of oxygen. In contrast, at high O2 ration of the cell (divided and undivided cells) has to be considered
overvoltage anodes, higher current densities may be applied with in the reactor design. In divided cells, the anolyte and catholyte
minimal contribution from the oxygen evolution side reaction. In are separated by a porous diaphragm or an ion conducting mem-
view of the afore mentioned facts, high O2 overvoltage anodes brane. For divided cells the choice of the separating diaphragm or
are usually preferred. In particular, boron-doped diamond (BDD) membrane is as important as the appropriate choice of electrode
anodes have been reported to yield higher organic oxidation rates materials for proper functioning of the electrolytic process. Over-
and greater current efficiencies than other commonly used metal all, the use of divided cells should be avoided whenever possible,
oxides such as PbO2 9 and Ti/SnO2 -Sb2 O5 .10 because separators are costly and tightening of a divided cell

Divided cell
Cell configuration
Undivided cell

Parallel plates

Static electrodes Concentric cylinders

2-dimensional Stacked discs

REACTOR DESIGN

electrodes
Parallel plates
Moving electrodes
Rotating electrodes
Electrode
configuration
Porous electrodes
Static electrodes
Packed bed electrodes
3-dimensional
electrodes
Active fluidized bed
Moving electrodes electrodes

Moving bed electrodes

Plug flow

Flow type
Perfect mixing
1749

Figure 3. Classification of electrochemical reactors in terms of cell configuration, electrode geometry and flow type.

J Chem Technol Biotechnol 2009; 84: 1747–1755

c 2009 Society of Chemical Industry www.interscience.wiley.com/jctb
 www.soci.org Á Anglada, A Urtiaga, I Ortiz

(reduction of electrode gap) is difficult and encounters a host of oxidation of waste-waters. In chloride mediated reactions, the
mechanical and corrosion problems.11 pH value may affect the oxidation rate because it determines
In the case of flow characteristics within a reactor, two types the primary active chloro species that is present in the effluent.
of limiting hydrodynamic behaviour may be considered, namely, During indirect oxidation, chlorine evolution occurs at the anode
plug flow and perfect mixing. (Equation (4)). At pH values lower than 3.3, the primary active
chloro species is Cl2 while at higher pH values its diffusion away
Operating conditions from the anode is coupled to its disproportionation reaction
Among the variables that are usually modified in electrochemical to form HClO at pH<7.5 (Equation (5)) and ClO− at pH>7.5
oxidation processes, the current density (intensity per unit area of (Equation (6)). In principle, operation at strongly acidic conditions
electrode) may be the term most frequently referred to because it would be considered to be the best option as chlorine is the
controls the reaction rate. It should be highlighted that an increase strongest oxidant followed by HClO.15 However, the system setup
in current density does not necessarily result in an increase in the usually employed in electrochemical oxidation of waste-waters
oxidation efficiency or oxidation rate and that for a given anode promotes its desorption, hindering its action as an oxidizing agent.
material, the effect of current density on the treatment efficiency Consequently, higher pH values would theoretically enhance the
depends on the characteristics of the effluent to be treated. electro-oxidation of pollutants, as HClO and ClO− are almost
However, the use of higher current densities usually results in unaffected by desorption of gases and they can act as oxidizing
higher operating costs due to the increase in energy consumption. reagents in the total volume of waste-water.14
In contrast to current density, the effect of temperature on
the overall efficiency of the electro-oxidation process has not Cl− −−−→ 1/2 Cl2 + e− (4)
been widely studied. It is generally acknowledged that direct Cl2 + H2 O −−−→ HOCl + H+ + Cl− (5)
oxidation processes remain almost unaffected by temperature − +
HOCl −−−→ OCl + H (6)
whereas mediated oxidation processes do not.14 An improvement
with increasing temperature of the mediated oxidation processes
by inorganic electrogenerated reagents (active chlorine, perox- MEASUREMENT OF PROCESS EFFICIENCY
odisulfate) has been reported. Nevertheless, operation at ambient In electrochemical oxidation of waste-waters, the technical
temperature is usually preferred as it provides electrochemical feasibility of the process is evaluated as usual, in terms of the
processes with lower temperature requirements than those of percentage removal of pollutant reached, while the economic
the equivalent non-electrochemical counterparts (i.e. incineration, feasibility is determined by the specific energy consumption. The
supercritical oxidation). decrease in pollutant concentration during electro-oxidation of
The physico-chemical characteristics of the waste-water (nature waste-waters, as well as the evolution of any other parameter
and concentration of electrolyte, pH value and concentration during the process, can be represented against time or as a
of target pollutants) also affect the electrochemical oxidation function of the specific electrical charge:
process. Although no agreement has been reached on the effect
of the nature and concentration of electrolyte on the overall J·A·t
oxidation efficiency, it has to be kept in mind that the higher the Q= (7)
v
concentration of electrolyte, the higher the conductivity and
consequently the lower the cell voltage for a given current The rate of oxidation is determined from the concentration of
density. For this reason, electrochemical oxidation treatment is pollutant vs. time plot whereas the representation against Q
more convenient and cost effective when the waste-waters to be is a measure of the efficiency of the electro-oxidation process.
treated already have high salinity. Disparities between both types of graphs only arise when the
The pH value, like temperature, affects mostly indirect oxidation influence of the current density is studied. To illustrate this point,
processes. However, a review of previous publications does the evolution of the total organic carbon (TOC) concentration with
not allow a conclusion to be reached on whether increasing time and with Q during electrochemical oxidation of phenol by
or decreasing pH favours pollutant removal in electrochemical means of a BDD anode is given in Fig. 4. The effect of current

1.0 1.0

0.8 0.8
TOC/TOC0
TOC/TOC0

0.6 0.6

0.4 0.4
J
0.2 0.2
J

0.0 0.0
0 2 4 6 0 5 10 15 20 25 30
Time (h) Q (Ah/l)

Figure 4. TOC dimensionless concentration profiles during the electrochemical treatment of phenol at different current densities:
50 A m−2 , ◦
1750

300 A m−2 and  600 A m−2 . Initial conditions: [phenol] = 470 mg L−1 ; [Na2 SO4 ] = 5000 mg L−1 ; pH = 2.3; T = 20 ◦ C; v = 1 L; anode area = 70 cm2 .

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c 2009 Society of Chemical Industry J Chem Technol Biotechnol 2009; 84: 1747–1755
Contributions of electrochemical oxidation to waste-water treatment www.soci.org

density in the range 150–600 A m−2 is shown. It can be seen that APPLICATIONS OF ELECTROCHEMICAL
although an increase in current density results in higher oxidation OXIDATION
rates (plot versus t), the oxidation efficiency decreased when the The feasibility of electrochemical oxidation was first tested with
current density increased from 150 to 300 A m−2 . Moreover, it a wide variety of synthetic waste-waters containing a diversity
should be pointed out that the plots against Q constitute a means of target compounds. However, in recent years, research work
of comparing the efficiency of the process at different scales, where focusing on the treatment of actual waste-waters has increased.
different anode areas per volume of effluent (A/V) are employed.16 Overall, the aim of these studies was mainly, to eliminate non-
There are specific energetic parameters (instantaneous current
biodegradable and/or toxic organic pollutants and ammonia
efficiency (ICE), average current efficiency (ACE), electrochemical
nitrogen contained in the effluent. Elimination of nitrite and
oxidation index (EOI) and specific energy consumption (W)) that are
nitrate from waste-waters has also been studied, although to a
used to assess the energy efficiency of the process.7,17,18 Among
less extent. Moreover, several attempts have been made recently
these, ICE is often used and measures the amount of current
at removal of micro-contaminants such as pharmaceuticals and
intensity used on the destruction of the target pollutants, and the
endocrine disrupting chemicals.19,20 As these contaminants are
occurrence and importance of side reactions. The occurrence of
usually present in concentrations in the region µg L−1 , the
side reactions can have different effects on the value of the ICE:
achievement of high mass transfer rates in the electrochemical cell
whereas the evolution of oxygen leads to a reduction of the ICE
is of paramount importance and is one of the main issues that needs
value, the formation of electro-generated oxidants will only result
to be tackled before electrochemical oxidation can be applied
in a reduction of the ICE value when they do not contribute to the
successfully in this field. Last, but not least, microorganisms can
elimination of the target pollutant. An ICE value of 1 indicates that
be inactivated electrochemically21 directly or via the generation
the applied intensity is being used for the oxidation of the target
of ‘‘killer’’ agents such as ·OH. Coupling of elimination of refractory
pollutant completely.
pollutants with disinfection of waste-waters in a single treatment

 step poses an attractive compact alternative, especially in the
[P]t − [P]t+
t
ICE = nFv (8) field of water reclamation and reuse where effective elimination
I
t
of pathogens is crucial to protect public health. Reduction
of COD concentration from 3820 to 78 mg L−1 and complete
Finally, the energy consumption (W) is directly related to the
elimination of microorganisms (initial count of 180 CFU mL−1 )
specific electrical charge (Q, kAh m−3 ) and the cell potential (v):
during electrochemical oxidation of latex waste-water represents
an example of the versatility of this technique.22 Nevertheless,
W (kW hm−3 ) = Q · V (9)
although many experimental studies have been carried out in this
field, the majority have been performed at laboratory scale and
ADVANTAGES AND DISADVANTAGES only lately have investigations begun at pilot scale.15,23,24
The efficiency and flexibility of this technology has been proven
Electrochemical oxidation provides several advantages for the
with a wide diversity of effluents as shown in Table 2. The main
prevention and remedy of pollution problems. The inherent
conclusion drawn from these is that electrochemical oxidation
advantage is its environmental compatibility as it uses a clean
represents a useful solution when the presence of recalcitrant
reagent, the electron, and there is little or no need for addition
and toxic pollutants prevents the use of conventional biological
of chemicals. Likewise, electrochemical oxidation is generally
treatments. Under appropriate conditions complete elimination
characterized by simple equipment, easy operation and brief
of COD, colour, ammonia and microorganisms can be achieved. In
retention time. Other advantages include:12
contrast to other advanced oxidation processes such as ozonation
(1) Robustness: the reaction can be terminated easily in seconds and Fenton oxidation that have been proposed for the treatment
by cutting off the power and it can also be restarted quickly of refractory residues, electrochemical oxidation does not lead to
after an operation problem.
(2) Versatility: these processes can deal with many pollutants and
treat quantities from microlitres to millions of litres.
(3) Electrochemical processes often have lower temperature Table 2. Application of electrochemical oxidation in treatment of
waste-water
and pressure requirements than those of equivalent non-
electrochemical counterparts such as incineration and su- Type of wastewater Reference
percritical oxidation. As a consequence, volatilization and
discharge of un-reacted wastes is avoided. Chemical Industry:
(4) Amenability to automation: the electrical variables used Fine chemical industry 14,31
in electrochemical processes (I,v) are particularly suited to Pulp and Paper industry 28,41
facilitating data acquisition, process automation and control. Petrochemical industry 23,42
Pharmaceutical industry 42
The main drawback of this process is its high operating cost due Textile Industry 43,44,45
to the high energy consumption. Additionally, potential for the Tannery Industry 39,46,47
formation of chlorinated organics during indirect oxidation by Food Industry 48,49,50
active chlorine needs to be considered. Also, in order to apply Agro-Industry
this technology, the effluent has to be conducting. Unfortunately, Olive oil 25,51–55
not all waste streams will have sufficient conductance and the Dairy manure 56
addition of an electrolyte may be necessary. Moreover, electrode Landfill leachate 15,30,57
fouling may occur due to deposition of material on the electrode Urban wastewater 20,32,58
1751

surface.

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 www.soci.org Á Anglada, A Urtiaga, I Ortiz

Effluent
Electrooxidation Biological

Effluent
Biological Electrooxidation

Effluent
MBR Electrooxidation

Effluent
MBR RO Electrooxidation

Chemical Effluent
coagulation Electrooxidation MBR

Effluent
Electroenzymatic Electrooxidation

Figure 5. Flow sheets for electrochemical oxidation treatment of waste-waters.

oxidation is a technically feasible alternative to eliminate organic

pollutants. However, partial oxidation of ammonia to nitrate ions
has been reported. Deployment of electrochemical oxidation in
combination with ion exchange26 or reverse osmosis27 as a post-
treatment step could be a possible solution to this issue. Also,
high energy consumption is usually required limiting the further
full-scale commercial application. Two steps have been taken
to cut down treatment costs; (1) the use of this technology in
combination with other techniques as either a pre-treatment or
as a polishing step; (2) the use of renewable energy sources to
power electrochemical oxidation. Several flow sheets reported
for electro-oxidation-based wastewater treatment schemes are
shown in Fig. 5.
In this line of investigation, great effort is being put into the
integration of electrochemical oxidation with conventional bi-
ological processes. This system takes advantage of coupling a
biodegradation (reduction of operating cost) and a physicochem-
ical process (shorter retention time). When the effluent is first
subjected to electrochemical oxidation, biodegradability of the
organic pollutants is enhanced, improving the performance of
Figure 6. View of BDD electro-oxidation pilot plant in landfill leachate
the subsequent biological process.28 In contrast, application of
treatment facility at Meruelo (Cantabria, Spain). electrochemical oxidation as a polishing step has the object of
completely mineralizing the refractory organic matter remaining
in the effluent after biological treatment. Panizza et al.29 demon-
the accumulation of oxidation-refractory organics. For example, strated that integration of a biofilm airlift suspension (BAS) reactor
significant differences were observed in the percentage of COD with electro-oxidation by BDD anodes as a polishing step was
removal obtained by electrochemical oxidation by means of a an effective means of treating a mixture of naphtalenesulfonates
BDD anode, Fenton oxidation and ozonation of the effluent contained in the infiltration water of a contaminated industrial
of a fine chemical manufacturing plant. Although total COD site. A reduction in energy consumption from 80 to 61 kWh m−3
removal was obtained by electro-oxidation, 80% and 50% were was obtained after coupling the two processes. Other treatment
the highest COD removal percentages achieved by ozonation schemes that have been evaluated include: (1) electroenzymatic
and Fenton oxidation respectively.25 In this context, electro- oxidation followed by electrochemical oxidation;23 (2) membrane
oxidation has been successfully applied as a post-treatment to bioreactor (MBR) followed by electro-oxidation;30 (3) chemical
Fenton oxidation to eliminate residual organic matter16,25 and to coagulation followed by electro-oxidation and MBR;31 (4) MBR,
oxidize ammonia,16 as the Fenton process was ineffective in the reverse osmosis and final electrochemical oxidation of the RO
1752

abatement of this pollutant. This confirms that electrochemical concentrate.32

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Contributions of electrochemical oxidation to waste-water treatment www.soci.org

The encouraging results obtained so far during the treatment of reactor with 1.05 m2 of boron-doped diamond anodes. The overall
industrial wastes by combined methods involving electrochemical efficiency in the combined system was 99% organic matter
oxidation set the basis for future work. Development of a sustain- mineralisation: 50% of the initial TOC was degraded in the aerobic
able process based on the integration of efficient technologies is treatment, 35% in the Fenton process and the remaining 15% in
one of the key obstacles that have to be overcome before full-scale the electro-oxidation step. The ammonia removal efficiency was
implementation of electrochemical oxidation. Optimal treatment greater than 90%, of which 50% was due to the electrochemical
schemes will eventually be decided upon achieving discharge treatment, since the Fenton process was unable to reduce the
limits set by national or international environmental regulations ammonia concentration. The results were consistent with the
at a reasonable cost.33 predictions obtained from tests previously performed at laboratory
At any rate, the selection of the best option relies on a scale, showing the robustness of the system.16
thorough understanding of the behaviour of each technology,
described by means of suitable mathematical models and
parameters. In this context, several models have been developed
CONCLUSIONS
in recent years to describe the electrochemical treatment of
Enormous advances have taken place in the development of
waste-water containing organic pollutants and ammonia. One of
electrochemical oxidation processes for waste-water treatment.
the first models to describe the electrochemical oxidation of
Electrochemical oxidation processes have proven to be an
organic pollutants with non-active electrodes was developed
efficient and versatile technology able to handle a wide variety
by Comninellis’ group and only considered direct oxidation
of waste-waters. Nevertheless, to achieve an efficient and cost
of organic contaminants.34 The model, characterized by its
competitive treatment, the waste-water should have relatively
simplicity, has shown excellent agreement with experimental
high conductivity. Moreover, the advantage of coupling electron-
results obtained in the electro-oxidation by boron doped diamond
driven reactions (direct oxidation) with in situ generation of
anodes of synthetic solutions of single organic compounds.
oxidants (indirect oxidation) makes this technique an interesting
However, the model shows deviations when dealing with complex
treatment alternative. In contrast, other treatment processes
mixtures such as those found in landfill leachates,15 where the
that are being considered as a possible means of dealing
presence of electrogenerated secondary oxidants also contributes
to the overall kinetics. In contrast, the model developed by with refractory pollutants involve transportation and storage of
Szpyrkowiczs’ group was able to describe the decolouration of reactants and may cause, consequently, a significant problem for
textile wastewaters35 when mediated oxidation by active chlorine safe processing. The main obstacles to be overcome before the full-
occurred. Mathematical models that describe the combined scale implementation of electrochemical oxidation is the reduction
contribution of both mechanisms to the overall oxidation of of operating cost and the development of efficient and stable
organic pollutants have also been developed.36 electrode materials. Another major area for future research is the
As far as ammonia oxidation is concerned, empirical instead improvement of the electrocatalytic activity and electrochemical
of mathematical models have been mostly developed. Ammonia stability of the electrode materials for the development of better
oxidation is generally believed to occur through indirect oxidation and more cost-effective electrodes, which will result in lower
by active chlorine37,38 although some authors have observed that operational and capital costs.
direct and indirect ·OH oxidation may contribute to the overall
oxidation of this pollutant.39,40 Nonetheless, many of these models
still have to be validated for real waste-waters with complex ACKNOWLEDGEMENTS
and unknown detailed composition. During the treatment of The authors are grateful for the financial support provided by
real waste-waters, competitive reactions are known to occur at the MICINN under projects PET2007-0431, CTM2006-00317 and
the anode surface3,39 and the different species interact creating CTQ 2008-00690/PPQ. A. Anglada also thanks the MEC for a FPU
complex scenarios. Recent attempts have been made to describe research grant.
these complex scenarios15 but due to the extremely diverse
features of waste-waters and electrode materials, a universal
approach has yet to be found.
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