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Critical Reviews in Environmental Science and


Technology
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Electrochemical Advanced Oxidation Processes,


formation of halogenate and perhalogenate speciesa
critical review
a

M. E.H. Bergmann , A. S. Koparal & T. Iourtchouk

Departments of Electroengineering and Applied Biosciences and Process Technology ,


Anhalt University , Bernburger Str. 55, D-06366 Koethen/Anh, Germany Phone: +49(0)3496
67 2313 Fax: +49(0)3496 67 2313
b

Department of Environmental Engineering , Anadolu University , Eskiehir , Turkey Phone:


+90(0)222 3350580 ext 6406 Fax: +90(0)222 3350580 ext 6406
Accepted author version posted online: 20 Aug 2013.

To cite this article: Critical Reviews in Environmental Science and Technology (2013): Electrochemical Advanced Oxidation
Processes, formation of halogenate and perhalogenate speciesa critical review, Critical Reviews in Environmental Science
and Technology, DOI: 10.1080/10643389.2012.718948
To link to this article: http://dx.doi.org/10.1080/10643389.2012.718948

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Electrochemical Advanced Oxidation Processes, formation of halogenate and perhalogenate
species a critical review.

M.E.H. Bergmann*, A.S. Koparal** and T. Iourtchouk*


* Departments of Electroengineering and Applied Biosciences and Process Technology, Anhalt
University, Bernburger Str. 55, D-06366 Koethen/Anh., Germany Tel. +49(0)3496 67 2313, Fax:

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+49(0)3496 67 2642, E-mail: h.bergmann@emw.hs-anhalt.de, T.Yurchuk@emw.hs-anhalt.de


** Department of Environmental Engineering, Anadolu University, Eskiehir, Turkey

Tel. +90(0)222 3350580 ext 6406, Fax: +90(0)222 3239501, E-mail: askopara@anadolu.edu.tr
Abstract
Advanced Oxidation Processes (AOPs) are widely used and suggested for environmentally-oriented
applications. New combinations of single methods are described in literature. An overview about methods
is given focusing on innovative papers of the previous years. At the same time, there are an increasing
number of indications and evident demonstrations that the occurrence of harmful by-products is possible.
Chlorate, bromate and perchlorate belong to these by-products of inorganic nature. Corresponding cases
are considered and discussed. By studying Electrochemical Advanced Oxidation Processes (EAOPs) it
was found that radical generating electrodes show strong tendencies of chlorate and perchlorate
formation in aqueous systems containing chloride ions. Also, bromate and perbromate formation is
possible. Therefore, the authors propose these components as new inorganic criterions in
environmentally-oriented water treatment. A new project is described considering electrochemical
drinking water disinfection in close co-operation between researchers, health and water treatment officials
and cell producers.
Keywords
Electrochemical Advanced Oxidation Processes, disinfection by-products, chlorate, perchlorate, bromate,
perbromate

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1. INTRODUCTION
Advanced Oxidation Processes [1] are based on the application of highly-oxidative species such
as radicals. Mostly, they are aimed at treatment of organic compounds in aqueous waste systems.
There is no clear classification and terminology in AOPs and EAOPs. The principles for

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generating highly-oxidative compounds may be divided into physical, chemical and combined
(Fig. 1) but there are many overlapping cases during application. To generate species with high
oxidation potential, activation by application of energy is necessary. Typical technologies of
activation are electrical discharge processes, heat activation and chemical reaction paths,
catalytic reactions, illumination/irradiation, electrochemical activation, cavitation (ultrasonic and
hydrodynamic) and others. One of the most popular among these is electrochemical oxidation,
which produces highly-reactive radicals such as hydroxyl radicals:

OH- OH + e-

(1)

H2O OH + H+ + e-

(2)

For instance, the extraordinary high reactivity of hydroxyl radicals is shown in Table 1.
The terminus Electrochemical Advanced Oxidation Processes is related with the
discovery, study and application of boron doped diamond (BDD) anodes after the
publication of Marselli et al. in 2003 [2-4]. After initiation, intensive studies on BDD
electrodes for electrochemistry started worldwide. First research on fundamentals and

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possible applications was located in groups of Pleskov, Natishan, Morris, Swain, Martin,
Vinokur, Anderson, Kang, Comninellis, Fujushima, Einaga, Rao, Brillas, Ferro, Battisti,
Haenni, Panizza and many others. Especially the ability of BDD anodes to produce
hydroxyl and other radicals leaded to promising approaches for destructing organics in
waste systems, synthesizing oxidants in industrial scale and producing ozone for

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disinfection purposes as well as for electroanalysis and corrosion protection. A series of


books summarizes the state of manufacturing, property characterization and
applications [5-12]. The history is well described in [12]. BDD electrodes are currently
produced by six companies.
Nowadays, more and more papers are published dealing with new combinations such
as photoelectrocatalysis [13-14], Electro-Fenton [15], microwave-activated
electrochemistry [16], Photoelectro-Fenton [17-21], and many others.
EAOPs are able to mineralize organic material to relatively harmless substances: CO2,
N2 and other non-toxic compounds. Therefore, the overwhelming majority of studies
emphasize benefit of technology, i.e. detoxification of wastewaters, decolouring or
disinfection. However, a more careful consideration is necessary:

If the process is of environmental relevance, environment may be affected by


effluents in the case of incomplete conversion.
If the method is extended to drinking water, health of many people may be
directly affected.

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Moreover, mainly organic by-products are a subject of discussion [22-25]. Inorganic byproducts are usually not considered; bromate is an exceptional case.
Currently, new efforts are apparent to adapt principles of AOPs for drinking water
treatment (large variety of method combination, new materials etc.). As a logic

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consequence, search for disinfection by-products has to be enforced.

This paper is aimed to give a brief overview about the developments in the field of
EAOPs focusing on papers with overview character published in recent years.

Based on literature analysis and our own experimental results on Electrochemical


Advanced Oxidation Processes the authors underline the enlarged necessity in more
accurate studies for inorganic treatment by-products in aqueous systems and suggest
new inorganic assessment criterions as firstly mentioned in [26].

2. ELECTROCHEMICAL ADVANCED OXIDATION PROCESSES STATE OF THE


ART
2.1 Quick look to methods application emphasizing the target of treatment
To emphasize the benefit of EAOPs most of the papers are concerned with the
treatment targets, for example, decolouring and removal of odours, removal of
surfactants, general or special waste water and effluent treatment, detoxification and
disinfection. Sometimes treatment fields may overlap. The following citations describe
main subjects in more details.

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2.1.1 Decolouring
Colour is a sign of special constituent presence. If colour disappears the constituent
concentration decreases. It does not mean that the system is now harmless but
disappearance of colour is an indicator for oxidation reactions. Many papers can be

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mentioned to deal with EAOPs decolouring [27-38]. Two papers give an overview over
electrochemical decolouring processes [39,40].
Decolouring is also an indicator method for EAOPs. Often, Acid Blue 22, Acid Orange 7,
Acid Orange 52, Methylene Blue, Prussian Blue, Reactive Red, Acid Yellow 36,
Reactive Orange 122, and other systems (textile industries wastewaters, olive oil mill
wastewaters) are used for this purpose.

2.1.2 Treatment of waste, process and natural waters


The large amount of publications in these fields cannot be overseen. The reader has to
distinguish between pure fundamental and application-orientated studies. Five larger
overviews were presented [41-45].
Although sometimes reported, treatment of wastes at concentration in the range of g L-1
level and at large volume is not sophisticated because of consuming unacceptable
amount of energy and time. Consequently, low-concentrated systems (contaminant
concentration at mg L-1 and g L-1 level) are more suitable for economic treatment.
(Most guidelines and recommendations use mass concentration data related to one
Litre like mg L-1 and g L-1. Thats why these units are preferred in this paper).

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One possible classification of considered systems is the removal of contaminants such
as pharmaresidues, surfactants, herbicides and insecticides, and pathogens
(disinfection).

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2.1.3 Removal of pharmaresidues

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It is estimated that 10 % of medicals prescribed each year worldwide (hundred thousand tons)
are released to environment. Detected hormonal activities of pharmaresidues (endocrine
disruptors) from natural and drinking water [46-49] in animals and human beings reported in the
1990ies, which resulted in a high number of works dealing with EAOPs for pharmaceutical
residual removal [50-53]. The background was the insufficient treatment by conventional

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methods [54]. Mostly, model substances in mg L-1 range of concentrations are studied.
Representatives are Bisphenol A [55,56] , Ibuprofen [57], Fluoxeine and Metoprolol [58,59], and
others as summarized by Esplugas [60]. The problems are the same as mentioned above:
unknown intermediates may be formed at large extent. When process water at mg L-1 range of
concentration is treated, long treatment times are necessary. At g L-1 range analytical control
of educts and by-products complicates application. A new paper for instance describes and
quantifies mineralization of beta-blockers such as atenolol, metoprolol tartrate and propranolol
hydrochloride by Electro-Fenton and Photoelectro-Fenton including BDD application and solar
light photolysis. Aromatic intermediates and carboxylic acids like oxalic and oxamic were
temporarily found. Finally, inorganic substances (nitrate, ammonium etc.) remained in the
treated systems [61].
Although halogenates and perhalogenates are in the focus of this paper it must be
underlined that ammonium and nitrate have to be taken into consideration of potential
risks for environment. Ammonium is toxic for fish, and nitrate supports eutrophication.
Recently, Sirs and Brillas published a new review paper [62], see also [63] and Table 2.

2.1.4 Removal of surfactants and personal care products

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Surfactants in effluents from home chemicals and personal care products are usually
responsible for foam formation. Biological waste water treatment plants are not able to
remove them totally. Some studies suggest EAOPs for surfactant removal [84].
Widespread use is not known. Surfactants are sometimes considered as a common
group of pharmaceutical and personal care products [60].

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2.1.5 Removal of biocides/herbicides


Approximately 25 years ago, environmental problems brought agro-chemicals into the
focus of discussion. Nowadays, pesticides and herbicide degradation is widely studied
[85-86]. Problems lie in the complicated organic chemistry scheme during oxidation and
the formation of many by-products. Chloride addition accelerates degradation but
results in chlorinated by-product formation [85]. Therefore, new publications describe
techniques such as electrochemical oxidation using BDD anodes that are capable of the
total mineralization of organic contaminants [87]. In section 2.2.2.2. papers describing
degradation of several biocides/herbicides by the Electro-Fenton methods and its
modification are listed.

2.1.6 Disinfection
Besides process water from production or cleaning and rinsing processes, chiller waters
belong to this group of contaminated systems. Disinfection here is the main target of
treatment, just as the case in the disinfection of drinking water, swimming pool water
and other aqueous systems. Free available chlorine species (HOCl, OCl-) are formed

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from chlorine radicals and mainly responsible for the disinfection effect in waters

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containing chlorine [88-90]:

Cl- Cl + e-

(3)

Cl- + OH Cl + OH-

(4)

In waters free of chloride oxidants like H2O2 and ozone (formation reaction in section
6.1) may react with microorganisms.
For drinking water, strong regulations and approaches regarding (mainly) organic
disinfection by-products exist [91]. Bergmann et al. critically discuss Inline electrolysis
mechanisms for disinfection [92,93].

2.2 Quick look to methods application emphasizing the principle of treatment


2.2.1 Non-combined electrochemical methods
Electrochemists had to use platinum and lead dioxide electrodes for adjustment of high
oxidation potential (permanganate, peroxide, persulphate, and ozone generation,
chromium oxidation etc.) for a long time. Later, it was found that mixed oxide (MIO)
electrodes are also able to develop radical chemistry mechanisms. A characterisation
was published elsewhere [94-95]. A new challenge was the presentation of doped thin
film diamond electrode characterized by high chemical stability, large electrochemical
window and the possibility to operate anodically at potentials higher than 2 V (SHE)
[96]. Boron doped diamond electrodes are most common electrodes. Nearly one

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thousand papers were published studying properties of doped diamond electrodes and
their applicability [97-100]. Velegraki et al. studied toxicity test on water treated by
doped diamond electrodes. Their results showed that degradation by-products are
consistently more toxic than the parent compound even after deep oxidation [68].
Currently, many new projects are orientated to targeted ozone production on BDD

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anodes. Some combined or hybrid processes including electrochemical principles are


mentioned as follows.

2.2.2 Combined electrochemical methods


2.2.2.1 Electrochemistry-UV and electrochemistry-visible light
Photoelectrochemical treatment of solutions may influence the composition and reaction
scheme near the electrode and in the bulk of solution. For example, Xiao et al.
developed a unique photoelectrochemical process for the treatment of ammonia in
wastewater containing chloride ions by combined use of electrogenerated active
chlorine and photogenerated active radicals (UPE). In this process, first of all Cl- ions
were electrochemically oxidized to Cl2. Second step was Cl2 hydrolysation to generate
active chlorine. The last step was active chlorine dissociation to OH and Cl radicals
under UV irradiation in the UPE process. Thus, these in situ electrogenerated active
chlorine and photogenerated chlorine radicals were responsible for the synergistic effect

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on ammonia degradation [101]. Combination of these methods has been considered for
wastewater treatment by some researchers [102-112]. The use of visible light and
electrochemistry [113] is a relatively new combination.

2.2.2.2 Electro-Fenton and Anodic Fenton Treatment (AFT)

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Photolysis and ultrasound were not found effective alone, while photocatalysis or
assisted photochemistry need an additional reagent such as H2O2 or TiO2.
Electrochemistry was proposed to be a new Advanced Oxidation Process as an
alternative process to produce Fentons reagent in the bulk solution [114].
The so-called Fenton process is known from the 1890s. It includes generation of
hydroxyl radicals by reacting Fe2+ ions with hydrogen peroxide:

Fe2+ + H2O2 Fe3+ + OH + OH


(5)

In the Electro-Fenton process, hydrogen peroxide that is necessary for a Fenton


reaction effect is formed by cathodic reduction of dissolved oxygen:

O2 + 2H+ +2e H2O2

(6)

Oxidized Fe3+ may be again electrochemically reduced:

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Fe3+ + e Fe2+

(7).

More than a hundred papers exist in the field. Song studied Electro-Fenton systems to
demonstrate their efficiency in wastewater treatment as a representative of EAOPs

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[115]. Brillas (Chapter 17 in [12]), and Jiang and Zhang [116] summarize the state of the
art in wastewater treatment.

Important papers of the Brillas and Oturan groups on pharmaceutical residue treatment
are cited here in section 2.1.3. Recently, a lot of studies have been conducted on
Electro-Fenton application of wastewater treatment [117-124].
Treatment of biocides/herbicides has gained very high interest in many papers
published recently [125-130].

It is a logic conclusion that an Electro-Fenton process may be combined with direct


anodic or mediated oxidation of pollutants. Brillas and co-workers studied herbicide
destruction by applying this combination of methods [87].
When the Electro-Fenton process is carried out under highly acidic conditions (pH=2-3)
and with sacrifice iron electrode, the process is called Anodic Fenton Treatment (AFT)
[131]. The technology was mainly studied for biocide/herbicide destruction [132-137].

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Combination of Electro-Fenton processes with biochemistry results into the Bio-Electro-Fenton
process [138].

2.2.2.3 Ultrasound-Electrochemical Oxidation


Ultrasound- electrochemical oxidation (US-EC process) is one of the novel combined

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technologies. Researchers have shown the obvious enhancement on electrochemical


degradation of pollutants by ultrasound [139,140]. It is widely accepted that ultrasound
with low frequency cause physical effect which can clean electrode surface and improve
mass transport, while US with high frequency usually causes chemical effects, which
can produce active substances such as hydroxyl free radicals. In the article [140], Zhao
et al. mention an ultrasound enhanced electrochemical oxidation of phenol on borondoped diamond and Pt electrodes. The rate of electrochemical degradation of phenol
and current efficiency on both BDD and Pt electrodes can be enhanced with the help of
US. The enhancement effect on BDD is much more obvious than for Pt. Lower amount
of intermediates are produced with BDD than with Pt. In the presence of ultrasound, the
variety of intermediates does not change on both electrodes. However, production and
degradation rate of intermediates can be promoted by ultrasound, in particular on BDD
[139]. Ultrasonic assisted electrochemical oxidation was also used in many other
studies [141-146].
According to Compton et al., power ultrasound applied to boron-doped diamond
electrodes allows the electrochemical reduction of dioxygen to hydrogen peroxide under
conditions of extremely high rates of mass transport and in the presence of cavitation. A

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colorimetric test reaction with iodide13 was used to confirm the formation of hydrogen
peroxide after electrolysis. In contrast, under the same experimental conditions but
without electrolysis the sonolytic formation of H2O2 was found to be negligible [147].

2.2.2.4 Sonoelectro-Fenton

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Combined electrochemical technologies have gained major attention in recent years for
environmentally friendly wastewater treatment. Oturan et al. worked on a novel hybrid
technique, namely Sonoelectro-Fenton, based on the simultaneous action of ultrasonic waves and
Electro-Fenton using a 3D cathode. The method was used for the removal of organic pollutants
in aqueous medium. In this study, result showed that high performance arises from the coupling
between ultrasound irradiation and the in situ electrogeneration of Fentons reagent [148].
Martinez and Uribe [149] studied the enhanced degradation of azure B dye using a SonoelectroFenton process. Babuponnusami and Muthukumar [150] made a comparison between Fenton,
Electro-Fenton, Sonoelectro-Fenton and Photoelectro-Fenton by oxidizing phenol. The last two
methods showed higher reaction rates than the others.

2.2.2.5 Photoelectro-Fenton

By combining Electro-Fenton with photochemical technologies the so-called


Photoelectro-Fenton process can be defined as a relatively new method of EAOPs. Life
cycle assessment showed the advantage of Solar Photoelectro-Fenton over other
combined technologies if applicable [151]. Reactor design description and comparison

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with Electro-Fenton and Fenton technologies was presented by Ting and co-workers
using benzene sulfonic acid mineralization [152]. De Luna and co-workers studied the
acetaminophen degradation [19]. Recent advances in the field of synthetic dye
treatment were discussed by Peralta-Hernandez and co-workers [153].

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There are still other combined methods existing such as peroxy-coagulation [154, 155],
which cannot be discussed here in details but it becomes clear that the short overview
reveals the great importance of EAOPs. EAOPs belong to the most dynamically
developing technologies in chemical engineering. The number of papers is increasing
each year. Despite the academic character of many research papers it can be expected
that application of the technologies will significantly grow. Therefore, possible problems
and risks have to be controlled more systematically.

3 PROBLEMS OF ELECTROCHEMICAL ADVANCED OXIDATION PROCESSES

In this part in order to examine thoroughly the formation of inorganic by products that is
the particular purpose of this study, all the AOPs in which this problem generally occurs
must be considered. Although benefit from Electrochemical Advanced Oxidation
Processes appears to predominate, the methods are not unproblematic. In this section,
main problems of EAOPs are addressed. Besides the economy, first of all, occurrence
of by-products must be mentioned. Focusing on inorganic by-products halogenates and
perhalogenates are considered in particular. This question is not totally new. In drinking

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water disinfection limiting concentration values were defined in special rules for selected
halogenates. Perhalogenates are under discussion. Chlorate, bromate, perchlorate and
perbromate are the most important representatives of these substances. Therefore,
halogenate and perhalogenate formation potential is shown here using an extended
literature research. Then, the formation of halogenates and perhalogenates is

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demonstrated using electrochemical processes with BDD anodes (sections 4 and 5) as


an accepted method of EAOPs.

3.1 Economy
In the most published studies AOPs are proved to be able to oxidize components in
aqueous systems. Process efficiency is mostly not studied though simple calculation,
which often shows that the practical application is far from reality. So, it is necessary to
pay more attention to economical points. The biggest problem is formed by high
investment and energy costs in large scale application. Consequently, economical
considerations have to include

the volume or flow rate of treated system

the rates of reaction and mass transfer

the ratio of contaminant concentration to oxidant concentration

the chemical complexity of the treated system

the specific investment and treatment costs per mass or volume unit of treated
system at defined final concentration level

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Descriptively, electrode and photocatalytic processes depend on mass transfer from


and towards the reaction surface. Electrodes, catalysts and catalyst carriers should be
available and cheap. Recent work has been focused on economical consideration for

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special AOPs [156].

3.2 By-product formation


Many papers are structured according to the following the scheme: Application of a
selected treatment principle, analysis of the concentration of the main contaminant,
derivation of a pseudo-reaction order. (Due to big analysis problems only in rare cases
reaction mechanism based on measured products or intermediates are discussed.) This
approach is highly critical because nothing is mentioned about the environmentallyrelated properties of the system treated. In principle, it is known that in treatment
processes organic by-products can be formed, which are more dangerous than the
initial species [157,158]. Toxicological studies are rare in the field [159,160]. Control of
TOC decay and different toxicity measurements are methods to control the problem.
Little is known about certain inorganic by-products such as chlorite, chlorate and
perchlorate when waters having high importance with respect to environment or health
are treated. Occurrence of bromate in drinking water after ozonation is an old-familiar
problem; there are also efforts to overcome the problem [161,162]. Logic consideration

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leads one to the conclusion that the formation probability of similar by-products by
EAOPs is very high. Factors supporting this are

extremely high reaction rates in the range of 106-1010 M-1 s-1 for second-order
reaction constants (or conversion times in micro- and millisecond range),

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high treatment times as typical for technologies with recirculation solutions,


presence of halogen atoms or ions in compounds and solutions in significant
concentration.

Halogenide ions may be present prior to treatment or be released as a result of


oxidizing organics containing halogen atoms.

Papers mostly describe experiments for total conversion conducted over a longer period
of time. Table 3 contains some new selected publications with respect to anodic
oxidation processes using boron-doped diamond anodes, which are able to generate
OH radicals, H2O2, and ozone.
In drinking water disinfection, the residence time inside an electrochemical cell with
single pass (not the treatment time; that often continues many hours or even days after
passing through cell.) is usually in the range of one second. But in treatment systems
with recirculation, higher specific charge load may be reached. In addition, enlarged
perchlorate formation is observed if the anode generates radicals at a high extent [169].
Other typical systems of interest are sewage and industrial wastewaters, and bilge

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waters. Inorganic by-product formation is often neglected both by equipment producers
and users but publications of many authors demonstrate the high formation potential.

4. DEMONSTRATION OF HALOGENATE AND PERHALOGEATE FORMATION IN


LITERATURE

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4.1 Chlorate and perchlorate


Siddiqui found chlorate when chlorinated water was treated by ozone and H2O2/O3. The
carbonate radical supported chlorate formation [170]. Enlarged chlorate formation in
swimming pool water disinfected electrochemically was found recently [171,172].
Addition of chlorine from hypochlorite feedstock produced electrochemically seems to
be a general problem. For example, Stanford et al. mention the presence of chlorate
and perchlorate in hypochlorite solutions [173]. In addition, Garcia-Villanova et al.
reported the presence of chlorite and chlorate [174]. Van Hege [175] describes
experiments of BDD-based oxidation of reverse osmosis membrane is concentrated by
chlorate formation in mM concentration range. Dordjevic and co-authors [176]
measured OCl, ClO2, ClO2- and ClO3- electrolysing hypochlorite solution. Photolysis of
free chlorine species may form chlorate [177]. Chlorate was found in
photoelectrochemistry [178] and in photoelectrocatalytic treatment [179] etc. A series of
papers [180-182] deals with by-product formation effects when solutions containing
chlorine are illuminated.

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Dasgupta measured perchlorate after ozonation of hypochlorite solution [182]. Studies
and discussions on perchlorate in drinking water were published by Bull and co-workers
[183] and Urbansky [184]. Review books on perchlorate were published [185,186].
Perchlorate was found in drinking water simulating cathodic protection systems using
iron electrodes [187]. Dasgupta and co-workers [182] describe perchlorate formation

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during electric discharge in aerosols containing chloride and during ultrasonic treatment
of sea water. Kang et al. [188] studied photolytic perchlorate formation from oxychlorine
anions. It was even reported that perchlorate can be formed on illuminated wet beach
sand surfaces. More discussion is presented in [189].
Jung et al. [190] found chlorate and perchlorate in chloride electrolysis using Pt as the
anode material. Our previous studies mainly dealt with drinking water disinfection
[191,192]. Results were confirmed by Polcaro and co-workers [193,194] and in studies
by the Rodrigo group [195]. Presence of chloride is necessary for the formation of
chlorate and perchlorate; however, perchlorate is also formed starting, from
hypochlorous, chlorite and chlorate solutions [169] in electrochemical oxidation for
instance. Most of mechanisms have not been studied yet but probably chemical and
electrochemical steps form known and unknown intermediates and products. It is
noteworthy that the perchlorate problem is discussed in the U.S. for many years.
Several states set perchlorate limits for drinking water at g L-1 level. The compromise
USEPA advisory value is 15 g L-1. A review of electrochemical perchlorate formation
in drinking water was given by Bergmann et al. [196].

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4.2 Bromate and perbromate
By electrolysing bromide, bromine and bromate solutions on MIO and BDD anodes it
could be found that bromate is a typical product [197,198]. Even, perbromate was found
for the first time [199]. Echardt and Kornmller measured bromate in mg L-1 range of
concentration treating ballast water by electrolysis using BDD anodes [200]. Oh et al. do

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not recommend application of Ti/Pt electrodes in seawater electrolysis due to the


bromate formation potential [201]. They also found in their studies perchlorate at lower
concentration. Selcuk et al. studied bromate formation in photocatalysis [202,203].
The origin of bromate and perbromate is bromide being a constituent of many water
matrixes at g L-1 level. Because of high environmental importance [204] bromate
formation was even studied in natural waters [205].

It is well-understood that ozonation of water containing bromide ions is accompanied by


bromate formation [206]. Bromine may be implemented into several THMs during
drinking water treatment [207]. Xin et al. detected bromate at levels lower than 10g L-1
when Yangtze water was disinfected under routine conditions by applying dark
chlorination and UV/chlorination processes [208]. UV irradiation enhanced the decay of
free chlorine and the formation of bromate. This effect is known from disinfection
chemistry [209]:

2HOCl + HOBr BrO3- + 3H+ + 2 Cl-

(8).

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The formation of bromate in electrolytic chlorine production for disinfection purposes
was confirmed by Hutchinson and Weinberg et al., but the anodes used in the studies
were not of BDD type [210,211]. Bromate formation in hypochlorite solutions and water
treated with hypochlorite solutions was also reported by other authors [171,172].

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There is no information on inorganic by-product formation for oxidation technologies


using chloride addition to accelerate destruction of organics [165,212,213]. Acceleration
is realized by oxidizing chloride to chlorine, a highly-efficient oxidant [214]. In our
experiments, it could be shown that metoprolol can be quickly oxidized on BDD anodes
only in the presence of chloride. Chlorate and perchlorate were found as by-products.
More results are given in section 5.
Randazzo et al. found chlorate by destructing chlorinated aliphatic hydrocarbons on
BDD anodes [215].

5. TOXICITY OF CHLORATE AND PERCHLORATE, BROMATE AND


PERBROMATE - RULES AND REGULATIONS
5.1 Chlorate
Summaries of documents in terms of chlorate are available at the WHO websites.
Chlorate is suspected to damage red blood cells. In rats, carcinogenic effects were
observed. Mutagenic action was found in some cases. No long-term studies exist but
are in progress. Chlorate dose of 36 g/kg of body weight per day for 12 weeks did not
result in any adverse effects in human volunteers. A long-term study is in progress,

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which should provide more information on chronic exposure to chlorate. So, many
chlorate poisonings have been reported [216]. Symptoms are methaemoglobinaemia,
anuria, abdominal pain and renal failure. For an adult human, the oral lethal dose is
estimated to be 230 mg of chlorate per kg of body weight [217]. Six separate doses of
sodium chlorate were given to ten male volunteers following a rising-dose protocol,

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single doses of 0.01, 0.1, 0.5, 1.0, 1.8 and 2.4 mg of chlorate ion per litre in 1 litre of
drinking-water was ingested by each man. Due to very slight changes in group mean
serum bilirubin, iron and methaemoglobin, the authors concluded that they didnt have
adverse physiological effects. The tested highest dose found out as a single-dose
NOAEL is 2.4 mg L-1 (34 g/kg of body weight per day) [218].
Chlorate is nitrate reductase-deficient mutants for Aspergillus nidulans according to
Cove [219]. It has been also found out that there is a mutagenic effect of chlorate in
Chlamydomonas reinhardtii and Rhodobacter capsulatus. Chlorate failed to induce
mutations in the BA-13 strain of Salmonella typhimurium. According to Prieto and
Fernandez, significant increases in mutants were observed at concentrations of 45
mmol L-1 and above for C. reinhardtii [220]. Chromosomal abnormalities were not seen
neither in the micronucleus test nor in a cytogenetic assay in mouse bone marrow cells
following gavage dosing with chlorate [221]. Many other partially controversial
investigations on several organisms exist in the field.

WHO guidelines give recommendation of 0.7 mg L-1 for drinking water. In Switzerland,
not more than 200 g L-1 chlorate is allowed. German regulations limit chlorate

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concentration in order not to be higher than 5.4 % of added chlorine (in solid form).
Chlorate is a normal by-product in chlorine and chlorine/chlorine dioxide disinfection

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chemistry and must be tolerated at certain extent [222,223]:

2HOCl + OCl- ClO3- + 2H+ + 2Cl-

(9)

HOCl + ClO2- + OH- ClO3- + Cl- + H2O

(10)

In electrochemical chloride oxidation, chlorate may be formed both by electrochemical


and chemical mechanisms. In complex electrochemical systems, other mechanisms
exist, for example, if chlorine dioxide and ozone are intermediates for a brutto-reaction
[224]:

2ClO2 + O3 + H2O 2ClO3- + O2 + 2H+

(11).

5.2 Perchlorate
Except for the efforts in U.S. states and by EPA, no regulations and recommendation
exist for perchlorate. Perchlorate is a natural component of Chile fertilizers and potash
ore in the United States and Canada. (Recently, it was found even on Mars.) As
mentioned above perchlorate seems to be formed under photolytic and photocatalytic
conditions in nature [183]. Perchlorate is produced and used in explosives, rocket fuel,
fireworks and road flares. Incorrect waste management lead to environmental pollution.
Perchlorate was detected in a 2005 AWWA occurrence study in 26 states of the USA,

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mostly below 12 g L-1. The problem of contamination by fireworks [225] is probably
underestimated. The tetraedric structure of perchlorate is responsible for its relatively
high stability. Perchlorate is persistent in surface waters and underground aquifers for at
least several months. Based on the early studies of U.S. researchers perchlorate is now
a subject of ecotoxicology [226] and searched in many areas, such as surface waters

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[227], food and ingredients [228,229], fish and bird mortality [230,231].

Many experiments with animals have shown negative perchlorate uptake effects on
thyroid function [232,233]. On human exposure perchlorate inhibits iodine uptake thus
influence thyroid metabolism processes, inhibiting hormone production and supporting
cause thyroid cancer. Against this background, many publications deal with perchlorate
destruction using physical, physical-chemical, chemical and biological methods. They
are not considered in this paper. Some medical studies discussed the opposite.
Perchlorate was found in breast milk of mothers. Lower values of 100 g L-1 iodine
(WHO definition) were found in urine of 36% of woman under enlarged perchlorate
exposure. The discussion on setting perchlorate standards in the U.S. is in progress. 1
g L-1 levels for drinking water were requested by EPA scientists in 2002. According to
new information, in January, 2009, the Environmental Protection Agency (EPA)
released an interim drinking water health advisory of 15 parts of perchlorate for every
billion parts of water - based on the recommendation of the National Research Council
(NRC). This reference dose is an estimate of a daily oral exposure by the human
population (including sensitive subgroups) that is likely to be without a significant risk of

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deleterious effects during a lifetime. Perchlorate is known to affect the production of
thyroid hormones, which are considered critical for brain development.

There is not a single mechanism of perchlorate formation in technical electrochemical


processes and detailed information is not available. But it is a fact that those

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electrochemical electrodes with OH radical generation show preferred perchlorate


formation potential, higher by the factor of 1000 compared to BDD anodes with mixed
oxide anodes [234]. Radical formation is also possible on Pt, PbO2 anodes, and others.
Surprisingly, perchlorate was detected in water electrolysis using iron anodes with Mn
deposits, simulating processes of corrosion protection [235]. The reasons that
perchlorate was not discussed more seriously in the past were a low interest of AOPs
users and difficulties in analysis at g L-1 level. These difficulties are now overcome
[191,236,237]. By combining IC-MS/MS concentrations of 0.005 g L-1 are still
detectable.

5.3 Bromate and others


Bromate was able to cause kidney cancer in experiments with animals. WHO recommends 0.010
mg [bromate] L-1 as a limiting concentration. Mechanisms of bromate formation were presented
by Caizares and v. Gunten [238] for DOC-free waters. The mechanisms in electrochemical
formation of bromate and perbromate are not yet known.

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Finally, it must be mentioned that the by-product discussion is not only limited by
halogenates and perhalogenates. Electron transfer and radicals reactions are able to

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produce peroxodisulphate from hydrogensulphate ions [239,240]:

2HSO4- S2O82- + 2H+ + 2-

(12)

HSO4- + OH SO4- + H2O

(13)

2SO4- S2O82-

(14)

It was reported that peroxomonosulphate and peroxomonosulphate-based disinfectants


can cause dermatitis [241] and tubercolocidal activity [242].

6 EXPERIMENTAL CONDITIONS OF SELECTED ELECTROCHEMICAL STUDIES

Formation of inorganic by-products from EAOPs is relatively new and there is no


systematic experimental study in literature. Some researchers deal with the formation of
inorganic by-products as a marginal part of their EAOP application to water or
wastewater treatment. Therefore, experimental conditions of selected electrochemical
studies [234,243,244] for formation of chlorate, perchlorate, bromate and others have
been summarized in this section.
In laboratory-scale discontinuous experiments a cell working with a rotating anode
(mixed oxides, Pt or Condias BDD material on niobium) 4 mm above a cathode in a
thermostated dark glass cell (200 mL), mostly at 20C was used (Fig. 2a). The current

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density was varied between 50 A m-2 and 500 A m-2 treating artificial and real drinking
waters. Discontinuous mode of operation was applied in drinking water treatment
experiments. For discontinuous and continuous operation and for varying the chloride
concentration in experiments with a flow-through cell shown in Fig. 2b, a plastic
container (hard-plastic material) was filled by 300 L of drinking water and the water was

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pumped by a centrifugal pump continuously through a rotameter and then through the
CSEM electrolyser equipped with 2 pairs of 90mm diameter BDD electrodes
(conducting diamond on silicon). The electrodes had diamond layers in the m range
and boron content between 2000 and 4000 ppm. In discontinuous mode, water was
pumped by the same pump from the 300 L container through a rotameter and then
through the electrochemical reactor back to the container. Drinking water from the
regional Koethen waterworks without and with chloride addition was used: pH=7.4-7.9,
42-46 mg[Cl-] L-1, 145-165 mg[SO42-] L-1 , 10-13.9 mg [NO3-] L-1. Chemicals of analytical
purity and higher grade with relatively low impurity influence on UV spectra were used.
Analyses were performed by HPLC. Perchlorate was analysed using a Metrohm
Metrosep Dual 4 column. Mostly, nitrite, nitrate, chloride, hypochlorite, chlorite, chlorate
and sulphate have been analysed by IC (Knauer/Alltech system with Novasep A-2 anion
column and electrochemical detector). Samples were collected at pre-determined time
intervals, immediately diluted if necessary and analysed by ion chromatography (IC)
and partially by spectrophotometry. Samples for IC, if not analysed in the course of or
directly after the experiment, were frozen and analysed later. Experiments were
repeated at least for once. For studies of polarization curves, an EG&G potentiostat

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model 283 together with a rotating disc electrode stand (model 616) was used in IR
compensation mode. The anode was a 1cm2 BDD disc (Condias) on niobium. A
mercury oxide reference electrode in an outer beaker connected with a salt bridge
containing 0.25 M NaOH was used to measure the potential. The cathode was a 15 mm

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x 30 mm platinum sheet.

6.1 Chlorate and perchlorate formation


In all experiments using the BDD anodes, chlorate and perchlorate could be detected,
at very high flow rates or low charge in g L-1 range of concentration. Fig. 3
demonstrates high sensitivity of the HPLC analysis showing a perchlorate result at mg
L-1 level. For comparison, a peak response for perbromate at trace concentration level
is given. Both components are clearly distinguishable.

Fig. 4 shows results of 1.2 M sodium chloride/0.52 sodium sulphate electrolysis.


Chlorate is steadily formed and degraded finally to perchlorate. If the electrolysis time is
extended all chloride is reacted to perchlorate. This simple example shows that
treatment systems with recirculation have to be considered with more care because
DBP accumulation may occur. Balancing the Cl amount (not shown here) one obtains
that in principle all Cl is distributed between the species chloride, active chlorine,
chlorate and perchlorate at least for experiments mostly conducted at 200 A m-2. So,
chlorite and chlorine dioxide, if formed, are very short-lived. Stripping effects and

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aerosol formation are obviously marginal under these conditions. Small quantities of
chlorate and perchlorate may be reduced at the cathode (not shown here).

In continuous operation mode, even at residence times in the scale of few seconds
perchlorate was found in experiments using the technical cell and real drinking water.

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Compared with mixed oxide electrodes, chlorate formation in the experiments using
BDD anodes is more intensive when radical mechanisms are relevant. Because in
drinking water chlorate is limited by regulations the process must be controlled also with
respect to chlorate formation. More perchlorate was found at higher current densities
(Fig. 5) and lower flow rates in the experiments [234].
The influence of chloride ions is often not well-understood. Higher chloride
concentration (usually higher than 50 mg L-1) results in lower perchlorate formation in
continuous and discontinuous experiments if majority of chloride ions has not yet
reacted (at relatively small specific charge passed). This behaviour can be explained by
species competition (Cl-, OCl-, ClO3- and others) for the relatively small number of active
sites on the BDD surface or reaction partners in the electrolyte layer and has been
recently discussed [245]. Another reason is the different reactivity of educts and
intermediates with OH radicals. For example, the rate constant for chlorate oxidation by
OH is thousandfold lower than that of chloride oxidation. As mentioned above, when all
chloride is finally converted to perchlorate (at relatively high specific charge passed),
perchlorate concentration again follows the chloride concentration).

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Chlorate concentration usually follows the chlorine concentration (Fig. 6). Extending the
experiment toward longer times the typical maximum (Fig. 4) reveals.

Finally, chlorate and perchlorate were found in discontinuous experiments using Pt and
mixed oxide anodes. This is consistent with other research results describing the

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occurrence of radicals and O3 at MIO, PbO2, Pt, and other anode materials [95,246].
Results are not presented here because these electrode material applications do not
classically belong to Electrochemical Advanced Oxidation Processes.

It was discussed above that there is no mechanism to explain perchlorate formation


starting from chloride. At least, following fundamental mechanism steps have to be
taken into account:

- Electrochemical electron transfer reactions


- Chemical reactions with radicals
- Disproportion reactions
- Chemical reactions with ozone

Their probability of occurrence depends on the electrode material, electrode potential,


pH, water matrix and concentration levels.

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Fig. 7 represents an anodic polarization curve for BDD. Regions for OH and beginning
dioxygen and ozone formation are indicated. The role of OH and O radicals depends
on many factors; the subject is still under discussion.
The reaction scheme (Eqs. 15-18) for BDD anodes is accepted [3,8] but this does not
mean that all reaction will proceed if the electrode potential is chosen sufficiently high.

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When for example enough reactive species are in the vicinity of OH generating active
sites they would react with OH radicals and O, and no ozone would be formed.
Moreover, other radicals may be formed as shown by radiolysis experiments.

OH O + H+ + e

(15)

O + O2 O3

(16) 2O

O2

(17)

2OH H2O2

(18)

The extremely low concentration of species such as chloride, hypochlorite and


hypochlorous acid, and chlorate (thousandfold lower than water molecules) let us
conclude that water molecules preferably react at the anode with OH and O radical
formation, whereas the participation of O radicals in the stepwise perchlorate formation
(Eq. 19) is still speculative. Other chemical reactions are mentioned in [196] but, for
example, chemical chlorate formation is by many orders of magnitude lower than a
radical-based chemistry, comparing corresponding rate constants.

OH, e-

OH, e-

OH, e32

e-, OH

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Cl-

(O, Cl)

OCl-

(O)

ClO2-

(O)

ClO3-

(O)

ClO4-

(19)

The intermediates Cl, OCl, ClO3 are not shown but their potential existence was
described in other publications. In [196] it was concluded that obviously OH does not
react with the chlorate radical due to the relatively low rate constant. New results seem

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to confirm this [247].

6.2 Bromate and perbromate formation


Generally, it is difficult to separate bromate from drinking water matrices. To overcome
the problem, minimization of bromate formation is the method of choice [248]. In
contrast to ozonation, electrochemical bromate and perbromate formation is not wellstudied. Several authors investigated electrode processes against the background of
bromate production. Ferro and co-workers studied the kinetics of Br- and Br3- oxidation
on Pt [249]. In dealing with BDD anodes, Ferro concluded that bromide oxidation is
mass transfer-controlled [250]. Cettou and co-workers [251] discuss bromate formation
by addition of the O radical to the hypobromite ion at Ti/RuO2 anode:

BrO- + 2O BrO3-

(20).

The authors recently studied [244] bromide and bromate electrolysis in drinking water
and synthetic aqueous solutions. The chosen range of current density was 50-500 A m2

, the range of bromide concentration was 1-1000 mg L-1. A boron doped diamond

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electrode was used in the discontinuous experiments. Even at small bromide
concentration of 1 mg L-1 bromate could be detected by ion chromatography, whereas
perbromate has not been found in systems with bromide concentrations as typical for
drinking water. Usually current efficiency in electrolysis of artificial solutions containing
about 100 mg L-1 bromide or more is lower than 1%. Fig. 8 describes bromate formation

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in regional drinking water at 5 mg[Br-] L-1 and for relatively low specific charge passed.
Additionally, curves for chlorine, chlorate and perchlorate formation are given. Probably,
kinetic effects, which are not yet known in detail, prevent bromate oxidation to
perbromate [244]. Nevertheless, the potential of perbromate formation on BDD anodes
has been clearly demonstrated and confirmed by Sez and co- workers [252].

Fig. 9 depicts concentration profiles for bromide, bromine, bromate and perbromate for
another experiment electrolysing bromide at 288.8 mg L-1. Only small charge amount is
separated for perbromate formation. Bromate is the main product.

In a first approach, possible mechanisms as shown in Eq. 21 form bromate and


perbromate

Br-

OH, O
-

e , Br

OBr-

BrO2-

BrO3-

Br
-

e , OH

BrO3

OH

BrO4-

(21)

But more studies are necessary for clarifications of mechanisms.

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7 AVOIDING HEALTH RISKS, FIRST STEPS
Apart from the U.S. with the perchlorate discussion there, no great awareness with
respect to perhalogenates as by-products in AOP exists worldwide. Because drinking
water treatment is of exceptionally high importance, systematic studies on direct
electrochemical disinfection have been carried out by our research group in a current

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co-operation research project [26]. Main subjects have been

- the study of electrode materials focusing on mixed oxide and BDD anodes,
- definitions of disinfection by-product classes,
- microbiological studies,
- kinetics studies (chemical and electrochemical reaction),
- mathematical modelling
- construction details.

Concluding the results a new project conception for deeper understanding of water
electrolysis effects has been worked out. The main idea is to establish normative
controlling methods and administrative regulations for a better control. At present, Inline
electrolysis of drinking water is not accepted in all European countries. Project structure
is given in Fig. 10. Detailed results will be published soon. Both laboratory-scale and
technical cell were studied under largely varied water conditions. Disinfection ability was
generally confirmed using Escherichia coli, Enterococcus faecium and the
bacteriophages MS1 and PRD1.

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Inorganic and organic by-products were analyzed. Cytotoxicity (necrosis, ROS
formation) and genotoxicity measurements (Ames test, micro nucleus) showed mainly
negative results for selected water types and treatment conditions.
Bromate formation can be expected if the bromide concentration is not exactly limited.
Thus, inorganic treatment by-products should be more in the focus of studies of AOPs

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and should serve as criterions for the efficiency and environmental importance of the
treatment method chosen. This approach is in agreement with suggestions of v. Gunten
et al. [253] discussing THM and bromate formation in drinking water ozonation.

8 CONCLUSIONS
EAOPs are a powerful instrument in environmental protection but they are not a priori
environmentally friendly methods. As a result of literature research and application of
special methods of AO the suspicion of by-product formation was confirmed.
Consequently, environmentally-oriented processes must be controlled with respect to
by-products with toxicity potential [198].

When chloride ions are present, formation of chlorate and perchlorate is possible. Thus,
chlorate and perchlorate may be used as new assessment parameters for an
environmentally friendly process. In presence of bromide ions bromate formation is the
most probable reaction generating unwanted by-products.

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The chlorate and perchlorate formation is high if the OH generation rate is high, higher
electrode potentials in electrochemical systems and recirculation are used. At higher
chloride concentration, lower perchlorate formation is possible at short-term treatment.

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Additional ions may influence the mechanisms by radical consumption.

In drinking water treatment processes [263] radical generating technologies should be


avoided.

Technical cells, which are a subject of a new scientific-technical co-operation project


that was finished recently, should be controlled by standard test methods.

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Table 1 Reactivity of hydroxyl radicals: Kinetic constants reported in literature for second order
reactions of the type Y + OH products
(A) Inorganic Reactions
Y
ClOClHOCl
ClO2 ClO2
ClO3 Brk
30.116.11.4< 1x
0.119x109
-1 -1
9
9
9
9
6
(M s )
4.3x10
0.14x10
7.9x10
4.4x10
10
1x1010
Y
OH
H2O2
HSO4 CO32HCO3NO2SCNk
3.525.2x109 2.7x107
8.5 x106 3.6x109 6.6x109
(M-1s-1)
4.7x105
3.9x108
(B) Organic Reactions
Y
Benzene
ChlorobenNitroben-zene Benzoate
Cyclo-hexane
zene
ion
k (M-1s-1)
6.7x109
6.2x109
2.2x109
5.6x109
6.71.5x109
Y
Methanol
Ethanol
n-Butanol
Acetate
Formate ion
ion
k (M-1s-1)
8.5x108
18.5x108
3.7x109
7x107
2.8x109
Y
Oxalic ion
Acetone
Neopentane
Cyclon-Hexane
pentane
k (M-1s-1)
1x107
7x107
0.980.16x109 4.46
5.61.1 x109
0.27x109
Y
2,3Ethene
2-Methyl-2Isoprene
2,3Dimethylbutane
Dimethyl-2butane
butane
k (M-1s-1)
4.81.0x109 7.71.6x109
876x109
939x109 1228x109
Y
n-Butane
Propene
n-Propanol
Gly
Glyk (M-1s-1)
2.6x109
2.5-2.6x108
15x108
1.7x107
1.9x109
Y
PharmaCarbamapara-ChloroBezafiDiazepam
ceuticals
zepine
benzoic acid
brate
k (M-1s-1)
3-10x109
8.8x109
5x109
7.41.2
7.21.0x109
9
x10
Y
Diclofenac
17-Ethinyl- Ibuprofen
IoproSulfameestradiol
mide
thoxazole
-1 -1
9
9
k (M s )
7.51.5
9.81.2x10
7.41.2x10
3.30.6
5.50.7x109
9
9
x10
x10
Y
Atrazine
MTBE
PerchloroTrichloro- Naproxen
ethylene
ethylene
k (M-1s-1)
2.4 x109
1.6 x109
2-3x109
3-4x109
9.60.5x109

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Table 2 State of publications related with pharmaceutical residues and their

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treatment mainly by EAOPs

Subject of consideration
Pharmaceutical residues and the
environment
Overviews over treatment technologies
Treatment of personal care products and
antibiotics
Removal of painkillers
Abatement of beta-blockers
Destruction of endocrine disruptors
Treatment of anti-inflammatory drugs

References
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[53], [63]
[60], [65], [66], [67], [68], [69]
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Table 3 Selected examples of studies on Electrochemical Advanced Oxidation


Processes using BDD anodes and applying higher specific charge.

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Species to be oxidized

Typical range of
specific charge, Ah L-1
Herbizides
20
Phenolic wastewaters
30
Benzyl alcohol
40
Alkohols, carboxylic acids
60
Alizarin Red
28
Clofibric acid
20
Anionic tensides
35
Oxalic acid
30
Bisphenol A
10
Phenol
50
Tannery wastewaters
40

85

Literature
87
163
164
165
30
17
84
166
56
167
168

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Figure captions
Fig. 1 Main principles and methods of generating highly-oxidative compounds by AOPs.
Fig. 2 Electrochemical stands used in experiments described (a) cell with rotating anode (1Mercotac rotating contact, 2 Medingen stirrer, 3 thermostated 200 mL beaker, 4 IrO2 or
IrO2/RuO2 expended mesh cathode at 4-5 mm distance, 5 10 cm rotating anode at 300 rpm). (b)
1 stirrer, 2 300 L container, 3 centrifugal Grundfoss pump, 4 regulating valve, 5 rotameter, 6
CSEM bipolar stack cell, 7 container.
Fig. 3 Perchlorate and perbromate detection by HPLC using a Metrohm Metrosep Dual 4
column.
Fig. 4 Chlorate and perchlorate formation in discontinuous electrolysis using synthetic solution
(45 mg[Cl-] L-1 (1.2 mM) + 50 mg[SO42-] L-1 (0.52 mM) on BDD anode (cell with rotating
anode, rotation rate 300 rpm, 50% IrO2/50% RuO2 cathode, current density 200 A m-2, volume
0.1 L, 20C).
Fig. 5 Perchlorate formation in a CSEM bipolar semi-technical cell using real drinking water
(BDD electrodes, flow rate 200 L h-1, temperature 23C, chloride concentration 43 mg L-1 or
1.21 mM).
Fig. 6 Chlorate formation in discontinuous electrolysis in drinking water
(35 mg[Cl-] L-1 (1 mM), 195 mg[SO42-] L-1 (2.03 mM) and 14 mg[NO3-] L-1 (0.22 mM)) with
and without addition of chloride on BDD anode (cell with rotating anode, rotation rate 300 rpm,
50% IrO2/50% RuO2 cathode, current density 200 A m-2, volume 0.1 L, 20C).
Fig. 7 Anodic polarization curves on rotating BDD anodic (temperature 20C, rotation rate
500rpm, scan rate 20 mV s-1, IR compensation, 1000 mg[NO3 -] L-1 + 250 mg[Cl-] L-1, sodium
salts).
Fig. 8 Chlorine, chlorate, perchlorate and bromate formation in discontinuous electrolysis using
drinking water (35 mg[Cl-] L-1 (1 mM), 195 mg[SO42-] L-1 (2.03 mM) and 14 mg[NO3 -]L-1 (0.22
mM)) with addition of bromide - 5 mgL-1 (0.06 mM) on BDD anode (cell with rotating anode,
rotation rate 300 rpm, 50% IrO2/50% RuO2 cathode, current density 200 A m-2, volume 0.1 L,
20C).
Fig. 9 Bromine, bromate and perbromate formation in discontinuous electrolysis in synthetic
solution ([Br-]=288mg L-1 (3.6mM)) on BDD anode (cell with rotating anode, rotation rate 300
rpm, 50% IrO2/50% RuO2 cathode, current density 300 A m-2, volume 0.1 L, 20C).
Fig. 10 Structure and topics of a current project for safer drinking water by inline electrolysis

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AOPs
Physically-induced

Chemically-based
Incineration
O3 and/or H2O2
Peroxo-components etc.
Catalytical reactions
Sub-critical wet air
oxidation
Fenton processes

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Discharge processes
Irradiation/photolysis
Cavitation/Sonolysis

Combined Methods
stepwise or in situ
Photocatalysis
Electrochemistry
Electrophotocatalysis
Electro-Fenton
Sono-Fenton

Fig. 1 Main principles and methods of generating highly-oxidative compounds by


AOPs.

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1
1

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5
3

(a)

Fig. 2 Electrochemical stands used in experiments described (a) cell with rotating
anode (1-Mercotac rotating contact, 2 Medingen stirrer, 3 thermostated 200 mL beaker,
4 IrO2 or IrO2/RuO2 expended mesh cathode at 4-5 mm distance, 5 10 cm rotating
anode at 300 rpm). (b) 1 stirrer, 2 300 L container, 3 centrifugal Grundfoss pump, 4
regulating valve, 5 rotameter, 6 CSEM bipolar stack cell, 7 container.

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Conductivity

Cond

perbromate 0.510

uS/cm

9.6
9.5

9.3
perchlorate 0.021

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9.4

9.2
9.1
9.0
8.9
8.8
3

10

11

12 min

Fig. 3 Perchlorate and perbromate detection by HPLC using a Metrohm


Metrosep Dual 4 column.

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Fig. 4 Chlorate and perchlorate formation in discontinuous electrolysis using synthetic


solution (45 mg[Cl-] L-1 (1.2 mM) + 50 mg[SO42-] L-1 (0.52 mM) on BDD anode (cell with
rotating anode, rotation rate 300 rpm, 50% IrO2/50% RuO2 cathode, current density 200
A m-2, volume 0.1 L, 20C).

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1.60

1.20
2000

1.00

1500

0.80
0.60

1000
500

perchlorate

0.40

chlorate

0.20

0
0

200

-1

1.40

2500

Chlorate, mg L

Perchlorate, g L

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-1

3000

0.00
600

400
-2

Current density, A m

Fig. 5 Perchlorate formation in a CSEM bipolar semi-technical cell using real drinking
water (BDD electrodes, flow rate 200 L h-1, temperature 23C, chloride concentration 43
mg L-1 or 1.21 mM).

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20

Chlorate, mg L-1

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[Cl-]=35mg/L

16
[Cl-]=135mg/L

12

[Cl-]=250mg/L

0
0.00

0.05

0.10

0.15

0.20

Specific charge passed, Ah L-1

Fig. 6 Chlorate formation in discontinuous electrolysis in drinking water


(35 mg[Cl-] L-1 (1 mM), 195 mg[SO42-] L-1 (2.03 mM) and 14 mg[NO3-] L-1 (0.22 mM))
with and without addition of chloride on BDD anode (cell with rotating anode, rotation
rate 300 rpm, 50% IrO2/50% RuO2 cathode, current density 200 A m-2, volume 0.1 L,
20C).

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Current density, A cm-2

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0.08
0.07

O2

0.06
0.05

O3

0.04
0.03

OH

0.02
0.01

surface changes

0.00
1.6

1.8

2.2

2.4

2.6

2.8

Electrode potential, V (SHE)

Fig. 7 Anodic polarization curves on rotating BDD anodic (temperature 20C, rotation
rate 500rpm, scan rate 20 mV s-1, IR compensation, 1000 mg[NO3-] L-1 + 250 mg[Cl-] L1

, sodium salts).

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12

1.00

[Br-]=5mg/L

10
0.80

chlorate
perchlorate

-1

bromate

0.60

6
0.40

Bromate, mg L

Chlorine, chlorate, perchlorate, mg L-1

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chlorine

0.20
2

0
0.00

0.00
0.05

0.10

0.15

Specific charge passed, Ah L

0.20
-1

Fig. 8 Chlorine, chlorate, perchlorate and bromate formation in discontinuous


electrolysis using drinking water (35 mg[Cl-] L-1 (1 mM), 195 mg[SO42-] L-1 (2.03 mM) and
14 mg[NO3-]L-1 (0.22 mM)) with addition of bromide - 5 mgL-1 (0.06 mM) on BDD anode
(cell with rotating anode, rotation rate 300 rpm, 50% IrO2/50% RuO2 cathode, current
density 200 A m-2, volume 0.1 L, 20C).

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500

25

400

20

bromide
bromate

300

15

perbromate
bromine

200

10

100

0
0

Perbromate, bromine, mg L-1

Bromide, bromate, mg L-1

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Specific charge passed, Ah L -1

Fig. 9 Bromine, bromate and perbromate formation in discontinuous electrolysis in


synthetic solution ([Br-]=288mg L-1 (3.6mM)) on BDD anode (cell with rotating anode,
rotation rate 300 rpm, 50% IrO2/50% RuO2 cathode, current density 300 A m-2, volume
0.1 L, 20C).

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Industry

Water
Works
Association

Project
Save
Drinking
Water

Federal
Water
Authorities

Research
Centre,
University

Fig. 10 Structure and topics of a current project for safer drinking water by inline
electrolysis

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