Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 83:769776 (2008)

Perspective Advanced oxidation processes for water treatment: advances and trends for R&D
Christos Comninellis,1 Agnieszka Kapalka,1 Sixto Malato,2 Simon A Parsons,3 Ioannis Poulios4 and Dionissios Mantzavinos5
1 Ecole

Polytechnique Federale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, CH-1015 Lausanne, Switzerland Solar de Almera (CIEMAT), Carretera Senes, km 4, E-04200 Tabernas, Almera, Spain 3 Centre for Water Sciences, Craneld University, Craneld MK43 0AL, UK 4 Laboratory of Physical Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki, Greece 5 Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania, Greece
2 Plataforma

Abstract: Advanced oxidation comprises a range of similar but different chemical processes aimed at tackling pollution in water, air and soil. Over the past few decades, multidisciplinary research has been carried out to study a broad spectrum of topics such as understanding of process fundamentals, elucidation of kinetics and mechanisms, development of new materials, modelling, process integration and scale-up. This article identies and discusses certain directions that seem to advance R&D on advanced oxidation for water/wastewater treatment. 2008 Society of Chemical Industry

Keywords: advanced oxidation processes; research advances; water; treatment

INTRODUCTION Advances in chemical water and wastewater treatment have led to the development of methods termed advanced oxidation processes (AOPs) or technologies (AOTs). AOPs can be broadly dened as aqueous phase oxidation methods based on the intermediacy of highly reactive species such as (primarily but not exclusively) hydroxyl radicals in the mechanisms leading to the destruction of the target pollutant. Over the past 30 years, R&D concerning AOPs has been immense particularly for two reasons, namely (i) the diversity of technologies involved and (ii) the areas of potential application. Key AOPs include heterogeneous and homogeneous photocatalysis based on near ultraviolet (UV) or solar visible irradiation, electrolysis, ozonation, Fentons reagent, ultrasound (US) and wet air oxidation (WAO), while less conventional (and consequently less studied) but evolving processes include ionising radiation, microwaves, pulsed plasma and the ferrate reagent. Although water and wastewater treatment is by far the most common area for R&D, AOPs have also found applications as diverse as groundwater treatment, soil remediation, municipal wastewater sludge conditioning, ultrapure water production,

volatile organic compound treatment and odour control.1 The growing interest of academic and industrial communities in AOPs is reected in the increasing numbers of publications in several peer-reviewed journals, patents and international conferences dedicated to the environmental applications of AOPs. For example, over 4500 articles have been published in journals of the Science Citation Index between 2005 and 2007 dealing with processes such as photocatalysis, ozonation, Fenton reactions, WAO and US; about 25% of them are devoted to photocatalytic processes. Water treatment by means of AOPs constitutes a core theme of research covering areas such as: 1) industrial efuent treatment including, amongst others, distillery, agrochemical, kraft-bleaching, pulp and paper, textile dyehouse, oileld and metal-plating wastes; 2) hazardous efuent treatment including hospital and slaughterhouse wastes; 3) removal of pathogens and persistent, endocrinedisrupting pharmaceutical residues from municipal wastewater treatment plant (WWTP) efuents (i.e. after secondary treatment);

Correspondence to: Dionissios Mantzavinos, Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, GR-73100 Chania, Greece E-mail: mantzavi@mred.tuc.gr Contract/grant sponsor: European Commission (Research DG); contract/grant number: 036882 Contract/grant sponsor: Spanish Ministry of Education and Science; contract/grant number: CE-CSD2006-004 Contract/grant sponsor: Fonds National de la Suisse de la Recherche Scientique (Received 23 October 2007; revised version received 14 November 2007; accepted 22 November 2007) Published online 11 February 2008; DOI: 10.1002/jctb.1873

2008 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2008/$30.00

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4) removal of organic micro-pollutants such as pesticides and heavy metals such as arsenic and chromium from water; 5) conditioning and stabilisation of biological sludge from WWTPs. AOPs can provide effective technological solutions for water treatment. Such solutions are vital for supporting and enhancing the competitiveness of different industrial sectors, including the water technology sector, in the global market. The main goals of academic, research and industrial communities through the development and implementation of environmental applications of AOPs will be: 1) new concepts, processes and technologies in wastewater treatment with potential benets for the stable quality of efuents, energy and operational cost savings and the protection of the environment; 2) new sets of advanced standards for wastewater treatment; 3) new methodologies for the denition of wastewater treatment needs and framework conditions; 4) new know-how for contributing to enhancing the European water industry competitiveness. The aim of this perspective article is to highlight, through representative paradigms and case studies, some important directions concerning R&D on AOPs for water and wastewater treatment. The following directions are by no means exclusive and primarily reect the authors standpoints about current advances and future trends in water treatment: 1) development of new materials to promote efcient treatment; 2) strategies for process integration; 3) process scale-up and commercialisation; 4) targeting new classes of pollutants and contaminants.

towards organics oxidation and efcient use of electrical energy. BDD has been applied for the electrochemical treatment of synthetic and industrial (BASF, Germany) wastewater.2 The specic energy consumption during this treatment, in the absence of mass transport limitation (100% current efciency), was approximately 22 kWh kg1 COD. According to the generally accepted mechanism of EM, water is rstly discharged (at potentials above 1.23 V vs SHE (standard hydrogen electrode) under standard conditions) at the anode active sites (M), producing adsorbed hydroxyl radicals (M( OH)ads ) which are involved in the mineralisation of organic pollutants (R) in aqueous solutions: R(aq) + (n/2)M( OH)ads (n/2)M + mineralisation products + (n/2)H+ + (n/2)e (1)

where n is the number of electrons involved in the oxidation reaction of organics. However, reaction (1) is in competition with the side reaction of the anodic discharge of these radicals to form dioxygen: M( OH)ads M + (1/2)O2 + H+ + e (2)

BORON-DOPED DIAMOND: A PROMISING MATERIAL FOR ELECTROCHEMICAL MINERALISATION Advances in materials science have led to a whole range of new materials that nd applications in AOPs: from corrosion-resistant construction materials for WAO processes to inexpensive, stable and active heterogeneous, iron-based catalysts for Fenton-like reactions to nanomaterials with improved catalytic properties and to new anodic materials for electrochemical reactions. The electrochemical mineralisation (EM) of organic pollutants is a relatively new technology for the treatment of wastewaters of moderate concentration, i.e. chemical oxygen demand (COD) < 5 g L1 . The main advantage of this technology is that no chemicals are used. In fact, only electrical energy is consumed for the mineralisation of organic pollutants on high oxidation power anodes. An ideal anode for this type of treatment is the boron-doped diamond (BDD) electrode characterised by high reactivity
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The activity (rates of reactions (1) and (2)) of these electrogenerated hydroxyl radicals is strongly linked to their interaction with the anode surface. As a general rule, the weaker the interaction, the lower is the electrochemical activity towards oxygen evolution (high O2 over-voltage anodes) and the higher is the chemical reactivity toward organics oxidation. Based on this approach, we can classify the different anode materials according to their oxidation power in acid media as can be seen in Table 1. The oxidation potential of the anode (which corresponds to the onset potential of oxygen evolution) is directly related to the over-potential for oxygen evolution and to the adsorption enthalpy of hydroxyl radicals on the anode surface; that is, for a given anode material, the higher the O2 over-voltage, the higher is its oxidation power. A typical low oxidation power anode is the IrO2 based electrode. Concerning this anode, it has been demonstrated using differential electrochemical mass spectrometry that the interaction between IrO2 and hydroxyl radicals is so strong that a higher oxidation state oxide, IrO3 , can be formed.3 This higher oxide can act as a mediator for both organics oxidation and oxygen evolution.4 On the other hand, BDD is a typical high oxidation power anode. In fact, electron spin resonance measurements using 5,5-dimethyl-1-pyrrolineN-oxide (DMPO) as a spin trap have demonstrated the formation of quasi-free hydroxyl radicals on BDD.5 These electrogenerated hydroxyl radicals on the BDD anode are very reactive (owing to the weak BDDhydroxyl radical interaction) and can result in the mineralisation of organic compounds with high current efciency.
J Chem Technol Biotechnol 83:769776 (2008) DOI: 10.1002/jctb

Perspective
Table 1. Oxidation power of various anode materials used in EM process in acid media

Electrode RuO2TiO2 (DSACl2) IrO2Ta2O5 (DSAO2) Ti/Pt

Oxidation potential (V) 1.41.7 1.51.8

Over-potential of O2 evolution (V) 0.18 0.25

Adsorption enthalpy Oxidation of M-OH power of anode Chemisorption of OH radical

1.71.9 1.82.0

0.3

Ti/PbO2 Ti/SnO2Sb2O5 p-Si/BDD

0.5

1.92.2

0.7 Physisorption of OH radical

2.22.6

1.3

A kinetic model for the electrochemical mineralisation of organics on BDD anodes under a galvanostatic regime based on reactions (1) and (2) has been developed.6 This model, shown in Fig. 1, allows the prediction of the evolution of the instantaneous current efciency (ICE) and COD during the electrochemical treatment. Figure 2 shows both the experimental and predicted values (full line) of ICE and COD evolution with the specic electrical charge passed during the anodic oxidation of different classes of organic compounds (acetic acid, isopropanol, phenol, 4-chlorophenol, 2naphthol). This gure demonstrates that there is excellent agreement between the experimental data and predicted values from the proposed model, while the electrochemical treatment over BDD anodes seems not to depend on the chemical nature of the organic compound, thus making this material an excellent candidate for electrochemical water treatment. We wish to emphasise again that AOPs are likely to benet from several other exciting advances in materials science, and reference to new anodic

(a) COD0

A B Akm COD(t) = COD0 1 t VR

) ( - Ak V
m

COD(t) = COD0 exp

CODcr = iappl 4Fkm

t+

1-

0 (b) ICE (%) 100

o Qcr = icr

(1-) km

ICE = exp

( - Ak V

t+

1-

Figure 1. Kinetic model for EM on BDD anode. Evolution of (a) COD and (b) ICE as a function of time (or specic charge): A, charge transport control; B, mass transport control; COD0 , initial chemical oxygen demand; , ratio between applied and initial limiting current densities; A, anode area; km , mass transport coefcient; VR , liquid volume; F, Faradays constant; Qcr , critical specic charge.

2500 2000 COD (mg L-1) 1500 1000 500 0 0 5

ICE

1.0 0.8 0.6 0.4 0.2 0.0 0 5 10 15 Specific charge (Ah L-1)

10

15

materials for electrochemical reactions was given only as a paradigm. For example, TiO2 photocatalysis, which has been widely employed in water treatment, suffers a serious drawback in that only UVA irradiation can be used for catalyst photoactivation. Since solar irradiation reaching the surface of the earth contains only 35% UVA, it is of great interest to extend the absorbance wavelength range of TiO2 to the visible region without losing photocatalytic activity. This can be done by doping TiO2 with non-metallic elements such as nitrogen, sulfur, boron, carbon, selenium and others, and this constitutes a relatively new eld of research.7

Specific charge (Ah L-1)

Figure 2. Experimental (symbols) and predicted (solid line) results for COD and ICE (inset) evolution as a function of specic charge during EM of various organics on BDD anode (i = 238 A m2 , T = 25 C, electrolyte 1 mol L1 H2 SO4 ): , acetic acid; , isopropanol; , phenol; , 4-chlorophenol; , 2-naphthol.

CAN AOPS DO THE JOB ON THEIR OWN? It is generally believed that the efcacy of AOPs to treat a certain waste stream is a strong function of (i) the composition and concentration load of
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the stream in question and (ii) the treatment aim itself. In fact, the higher the polluting load and the extent of pollution removal needed, the more harsh the treatment conditions to be applied are. In this view, treatment performance can be enhanced through coupling various processes as follows. 1. Simultaneous application of different AOPs to promote the rate of organics oxidation. Typical examples include UV/H2 O2 , UV/ozone, ozone/H2 O2 , UV/ozone/H2 O2 , UV/TiO2 /H2 O2 , US/Fentons reagent, UV/Fentons reagent, WAO/H2 O2 , electrolysis/Fentons reagent and many more aimed at increasing the rate of reactive species formation compared with the respective individual processes. Interestingly, this type of combination may lead to treatment efciencies that are greater than the sum of efciencies that could be achieved by the individual processes applied alone. Coupling US irradiation with TiO2 photocatalysis (i.e. so-called sonophotocatalysis) is such an example of process synergy where the synergistic action of ultrasound may be associated with an increase in the production of hydroxyl radicals via water sonolysis as well as an increase in catalyst surface area. Moreover, the ultrasound may accelerate mass transfer of reagents onto the TiO2 surface as well as remove any impurities from its surface, both of which would also lead to increased degradation.8,9 2. Sequential application of various AOPs to enhance selectivity. This treatment strategy may be suitable for industrial efuents containing several classes of organics that exhibit different levels of oxidisability towards different reactive moieties. A typical recent example includes a two-stage treatment comprising Fenton oxidation followed by BDD electrochemical treatment for the complete mineralisation of olive mill efuents.10 Non-selective, hydroxyl radical-mediated Fenton oxidation was capable of reducing the initial polluting load to about 1 g L1 residual COD; this was refractory to further Fenton oxidation but could be mineralised by direct oxidation over the BDD surface as well as secondary oxidation reactions induced by other compounds electrochemically generated in the electrode. 3. Application of a separation treatment prior to AOP treatment to transfer pollutants from the liquid to another phase so that they can be treated more easily and do not intervene with advanced oxidation. For instance, efuents containing volatile organics or solids may rst be subjected respectively to processes such as stripping or coagulation, occulation, sedimentation and ltration to remove these compounds from the efuent prior to AOP treatment. Moreover, membrane modules and adsorption techniques may also be employed to remove dissolved contaminants that need to be treated separately or recovered as likely valuable by-products (i.e. waste valorisation).
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4. Application of AOPs as a pre-treatment stage to enhance biodegradability and reduce toxicity, followed by biological post-treatment. The concept of this approach, which has gained a lot of attention over the past several years, is relatively straightforward and based on the facts that (i) biological treatment is perhaps less costly and more environmentally friendly than any other destructive treatment and (ii) complete mineralisation by AOPs induces excessive treatment costs, since the highly oxidised end-products that are formed during chemical oxidation tend to be refractory to total oxidation by chemical means. These end-products, which are typically represented by short carboxylic acids, can, however, be degraded easily biologically.11 Putting these two observations together regarding the rate of CC bond scission by chemical and biological means, the concept of an integrated chemical and biological treatment process can be illustrated schematically as in Fig. 3.12 As seen, there appears to be a breakpoint beyond which biological treatment becomes more attractive than chemical oxidation in terms of rate and consequently efciency. 5. Complex treatments comprising various physical, advanced oxidation and biological processes. These are specic to the waste stream in question and usually applied to industrial efuents. Optimal treatment schemes will eventually be decided upon achieving discharge limits set by national or international environmental regulations at a reasonable cost. This, in turn, will be dictated by the type of waste stream to be treated, i.e. its composition, concentration, biodegradability and toxicity. In this respect the following generic decisionmaking strategies may be adopted. 1. If the wastewater is biodegradable, a biological treatment should be chosen unless discharge limits are already fullled regarding organic carbon content (TOC), toxicity and other physicochemical parameters (which is an unlikely case for

AOP or WAO Rate of carbon-carbon scission Effluent

Biodegradation Biogenic End products intermediates

Switch processes

Chemical oxidation

Biological

Molecular size
Figure 3. Concept of integrating AOP pre-treatment and biological post-treatment.

J Chem Technol Biotechnol 83:769776 (2008) DOI: 10.1002/jctb

Perspective

industrial wastewaters), because classical biological treatments are, at present, the cheapest and most environmentally compatible option. 2. If the wastewater is not biodegradable and its organic content is high (TOC > 0.1 g L1 ), an AOP pre-treatment before biological post-treatment should be envisaged. Following treatment, the efuent quality has to be checked to decide if it complies with legal requirements for efuent discharge. 3. If the wastewater is not biodegradable, its organic content is low (TOC < 0.1 g L1 ) but toxicity is still high, one should design an appropriate AOP treatment aimed at reducing toxicity. Subsequent biological treatment is not recommended, as the already AOP-treated efuent will possess little metabolic value for the micro-organisms. Very often this wastewater could be disposed of to the environment or sent to a public sewage treatment system for further polishing. 4. If the wastewater is not biodegradable, its TOC content and toxicity are low but other physicochemical requirements are not met (i.e. the efuent is coloured), an AOP treatment without subsequent bio-treatment should also be envisaged. After the AOP treatment the efuent quality has to be assessed before discharge.

PROCESS SCALE-UP AND COMMERCIALISATION: THE EXAMPLE OF SOLAR PHOTOCATALYSIS Since as early as the mid-1970s,13 photocatalytic detoxication has been discussed in the literature as an alternative method for cleaning up polluted water. However, industrial applications with solar energy, engineering systems and engineering design methodologies have only recently been developed. Until about a decade ago, only two engineering-scale demonstrations, one for groundwater treatment in the USA and another for industrial wastewater treatment in Spain (at Plataforma Solar de Almera), were known to exist. Since then, several installations have been constructed and various engineering systems have been developed. A laboratory-scale double skin sheet reactor (DSSR) was developed to treat biologically pre-treated industrial wastewater from the Volkswagen AG factories in Wolfsburg (Germany) and Taubat e (Brazil); the results of the experiments were so promising that a pilot plant was installed in the premises of the Wolfsburg factory in 1998. At about the same time a pilot study was carried out in several Mediterranean countries to develop the thin lm xed bed reactor (TFFBR). Based on these results, a pilot plant, nanced by the European Commission, was built at the site of a textile factory in Tunisia (Menzel Temime). Solar photocatalysis was also employed to treat onsite landll leachates; a pilot plant, also nanced by the European Commission (LIFEENVIRONMENT-LIFE99 ENV/Gr/000539), was
J Chem Technol Biotechnol 83:769776 (2008) DOI: 10.1002/jctb

constructed and operated in the sanitary landll site of Rethymnon (Crete, Greece). Under the SOLARDETOX project (Solar detoxication technology for the treatment of industrial non-biodegradable persistent chlorinated water contaminants) a consortium coordinated by Plataforma Solar de Almera (Spain) was formed in Europe for the development and marketing of solar detoxication of recalcitrant water contaminants.14 The main goal of the project (nanced by the EC-DGXII through the Brite Euram III Programme, 19972000, BRPR-CT97-0424) was to develop a commercial non-concentrating solar detoxication system using compound parabolic collector (CPC) technology. A full-size demonstration plant for eld demonstration to identify any pre- or post-processing requirements, potential operating problems and capital and operating costs was constructed at the facilities of HIDROCEN (Madrid, Spain). The same collectors have also been used to treat paper mill efuents in Brazil and Germany and paper mill efuents, surfactants and textile dyes in Spain. In 2004 a new CPC-based plant was installed in the context of a project focusing on problems in the rapidly growing, intensive greenhouse gas-producing agricultural sector in the Mediterranean basin.15 One of these problems is the uncontrolled dumping of plastic pesticide containers, which usually still contain residues. The solution is to selectively collect these containers for recycling. Plastic container recycling starts with shredding followed by industrial washing of the shredded plastic, which produces water polluted with highly toxic persistent compounds (pesticides + excipients). This hazardous water containing the dissolved toxic organic matter that was in the pesticide containers must be treated. This rinse water is then continuously recycled and reused. The ALBAIDA company and CIEMAT (Spain) jointly presented a project entitled Environmental collection and recycling of plastic pesticide bottles using advanced oxidation process driven by solar energy to the European LIFE-ENVIRONMENT programme, which was approved and began in October 2001. The plant is now in routine operation. The photo-Fenton treatment mineralises 80% of the TOC in the rinse water in a batch process. The total collector surface area is 150 m2 and the total photoreactor volume is 1.06 m3 . After treatment, iron needs not be removed, since the water is either reused or transferred to a 20 000 m3 irrigation pool and used as iron-rich greenhouse irrigation water. More recently (2006), a new step has been taken combining solar photo-Fenton and aerobic biological processes to successfully treat a saline industrial wastewater containing about 0.6 g L1 of the non-biodegradable compound -methylphenylglycine (MPG) and 0.40.6 g L1 TOC. It consists of a solar photo-Fenton reactor with 100 m2 of CPCs and an aerobic biological treatment plant based on an immobilised biomass activated sludge reactor of
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There is not a denite range of concentration of contaminants that could be considered appropriate for being treated by solar AOPs. A very high organic load would result in excessive operational costs associated with chemicals consumption (i.e. hydrogen peroxide). In this view the concentration range that could be considered non-optimal for solar AOPs is TOC > 1 g L1 (or COD > 2.5 g L1 ). On the other hand, solar AOPs would ideally be tted for efuents with TOC < 0.1 g L1 (or COD < 0.25 g L1 ). For < 0.1 < TOC < 1 g L1 (or < 0.25 < COD < 2.5 g L1 ), integrating solar AOPs and bio-treatment may be an ideal treatment option.

Figure 4. View of solar photo-Fenton unit (top) coupled with biological treatment (bottom) in Plataforma Solar de Almera, Spain.

1 m3 capacity (Fig. 4). The overall efciency in the combined system was about 95% mineralisation; 50% of the initial TOC was degraded in the photo-Fenton pre-treatment, while 45% was removed in the aerobic biological treatment.16 The degradation rate of pollutants is a key point for deciding if AOPs can be applied at industrial scale with reasonable cost.17 Coupling solar photoFenton and biological treatment at industrial scale to treat a wastewater at 630 m3 day1 ow rate (1260 kg COD day1 ) would cost about 7/m3 (or 3.5/kg COD). About 35% of this value is associated with the plants capital cost, which is directly proportional to the degradation kinetics of photo-Fenton, and 50% is related to hydrogen peroxide consumption, which is directly related to the concentration and type of pollutants. The reader should bear in mind that 1 m3 of the wastewater in question contains 2 kg of COD. Hence the cost per kg COD is half that per m3 and the treatment capacities with respect to kg COD are double the volumetric ones. This fact should be taken into account when considering treatment of wastewaters with different concentrations, which, as long as the qualitative chemical composition is similar, will yield similar performance with respect to gures of merit referring to COD.
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AOPS FOR MICRO-POLLUTION ABATEMENT AND DISINFECTION Micro-pollutants listed as emerging contaminants of concern to the water industry have traditionally included, amongst others, pesticides and their degradation by-products, disinfection by-products, organotins, algal toxins, perchlorate, Methyl tertiarybutyl ether (MTBE), nitrosamines, in particular nitrosodimethylamine, and brominated ame retardants. Pesticides have been widely employed since the 1950s and are particularly hazardous, as they are chemically developed to be toxic and, in some cases, persistent in the environment. Therefore it is not surprising that particular attention is being paid to developing methods for their removal from waters. The current best available technique for removing pesticides from water is either granular activated carbon (GAC) or GAC combined with ozone. However, AOPs such as UV/ozone, UV/H2 O2 , Fenton and photo-Fenton reactions, amongst others, have been tested and can now be considered a direct competitor to GAC processes for pesticide removal. A plant based on UV/H2 O2 treatment and designed to operate at a daily capacity of 95 000 m3 has recently been installed by PWN at Andijk (The Netherlands). The process achieves 80% atrazine degradation with a UV dose of 5.4 kJ m2 , 0.006 g L1 H2 O2 and an electrical energy consumption of 0.56 kWh m3 .18 Over the past few years, particular attention has been paid to the environmental monitoring and fate of the so-called endocrine-disrupting compounds (EDCs), i.e. persistent natural or synthetic molecules with various applications in the pharmaceutical sector that are often only partially removed from water in municipal wastewater treatment plants and consequently enter the environment. The fact that EDCs have only recently been recognised as environmental hazards is primarily due to the lack of sophisticated analytical protocols to detect them and their metabolites at low concentration levels; as the analytical constraints are removed, various treatment techniques, including AOPs, are expected to be developed.19,20 A recent work21 demonstrated the effective degradation of 17-ethinylestradiol, a synthetic oestrogen, by electrolysis over a titanium anode in different water
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matrices, i.e. tap water and a biologically treated hospital efuent. Optimal treatment conditions led to quantitative removal in both cases and also achieved adequate disinfection of the medical waste. This example also brings about the possibility of AOPs being used for water disinfection. In this view, three directions are envisaged. 1. Solar disinfection for potable water treatment. Sunlight may provide a low-cost, sustainable and simple method of treating contaminated drinking water in developing countries with consistently sunny climates under circumstances in which people have no access to alternative water treatment systems. At its simplest (batchwise process) the method involves lling a transparent vessel with water and then exposing it to full-strength sunlight for several hours to inactivate a wide range of microorganisms such as faecal indicator bacteria, waterborne pathogens, yeasts and moulds. Although sunlight may cause direct damage to bacteria, it is more common that it causes indirect effects through the excitation of photosensitisers, i.e. molecules that exist either in water as natural organic matter or within cells; these excited molecules can then either attack cells or react with water oxygen to form reactive species that in turn inactivate cells. Besides these photon-driven effects, inactivation may also be induced by thermal effects, thus mimicking pasteurisation. In addition to photosensitiser-based solar disinfection, photocatalysis over immobilised or suspended TiO2 has also been employed to destroy bacteria, viruses, fungi and protozoa. 2. Disinfection of biologically treated efuents in WWTPs. At present, the common practice to stabilise efuents subject to secondary treatment involves chlorination, an inexpensive and efcient method that causes permanent damage to microorganisms. A drawback of the process though has to do with the likely formation of organochlorinated by-products, which are consequently released to water receivers. Ozonation and UVC irradiation have been, to some extent, employed as alternative disinfection methods, while pilot trials have also been performed to assess electrolysis, US irradiation and TiO2 photocatalysis for secondary efuent disinfection. A major concern associated with the aforementioned AOPs is that, unlike chlorination, bacteria inactivation may not necessarily result in their permanent destruction, as they can partly regenerate during treatment. In addition, advanced oxidation to remove residual efuent organic matter is a new area of application should water reclamation and reuse for irrigation and other purposes become an option. 3. Treatment of hazardous hospital waste streams that may constitute a public health risk, especially for healthcare workers and hospital laboratory personnel. A recent example22 demonstrated the use of H2 O2 -enhanced TiO2 photocatalysis for
J Chem Technol Biotechnol 83:769776 (2008) DOI: 10.1002/jctb

the inactivation of prions known as transmissible spongiform encephalopathies (TSEs), including CreutzfeldtJakob disease (CJD) in humans, bovine spongiform encephalopathy (BSE) in cattle and scrapie in sheep and goats. Prions are unusually resistant to the conventional physical and chemical methods of decontamination (e.g. treatment with bleach containing active chlorine, exposure to formic acid and boiling with detergents or NaOH) commonly used to inactivate other infectious agents. Initial in vitro experiments followed by a bioassay with the scrapie strain 263K in Syrian hamsters indicated that TiO2 photocatalysis of scrapie-infected brain homogenates reduced infectivity titres signicantly (Fig. 5).

CLOSING REMARKS In general, AOPs are cheap to install (possibly with the exception of WAO units where special construction materials may be needed to withstand increased corrosion) but still expensive to operate owing to the usage of costly chemicals such as H2 O2 , increased energy consumption, etc. Cutting down treatment costs will make AOPs attractive to the water industry; a step in this direction is the use of renewable energy sources to power the processes as exemplied in the case of solar photocatalysis. Another step would be the use of AOPs only as a pre-treatment to improve the biodegradability of biorecalcitrant streams, thus permitting their disposal in a conventional municipal WWTP. Avoiding severe treatment conditions can also reduce operational (and capital) costs, and this is where environmental catalysis and materials science play an important role through the development of inexpensive, active, stable and recyclable catalytic materials. Although it is still a common perception that the sustainability of AOPs, or indeed any other technology, to treat waters and wastewaters is eventually dictated by process economics, the water industry and policy makers may have to reconsider given the growing problem of high-quality water shortage in arid and

Figure 5. Survival percentage as a function of post-inoculation time: , scrapie-infected brain homogenates; , photocatalytically treated scrapie-infected brain homogenates; , normal hamster brain homogenates.

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semi-arid areas in developing and developed countries, which is expected to worsen as a result of global climate changes. In other words, efuents have to be considered as a resource, permitting water reuse for different purposes (industrial process water, crop and garden irrigation, groundwater relling, etc.). The treatment of wastewaters that have been generated without the application of cleaner production and waste minimisation principles is a losing game, ultimately costing all parties materials and energy resources. With the continuous increase in polluted water ows the challenge arises to develop appropriate, innovative and integrated solutions such that the produced efuent not only meets requirements but can also be considered as a resource. This may require drastic and perhaps somewhat costly solutions based on technologies capable of cleaning up water polluted by persistent organic and other matter and/or contaminated by infectious micro-organisms. AOPs, either alone or in conjunction with other processes, can provide technically sound options to achieve this goal.

ACKNOWLEDGEMENTS S Malato wishes to thank the European Commission (Research DG) for nancial assistance within Global change and ecosystems of VI FP (contract 036882, INNOWATECH Project) and the Spanish Ministry of Education and Science (Programa Consolider Ingenio 2010 CE-CSD2006-004). C Comninellis and A Kapalka acknowledge nancial support from Fonds National Suisse de la Recherche Scientique.

REFERENCES
1 Parsons SA and Williams M, Introduction, in Advanced Oxidation Processes for Water and Wastewater Treatment, ed. by Parsons S. IWA Publishing, London, pp. 15 (2004). 2 Ouattara L, Chowdhry MM and Comninellis C, Electrochemical treatment of industrial wastewater. New Diam Front Carbon Technol 14:239247 (2004). 3 Fierro S, Nagel T, Baltruschat H and Comninellis C, Investigation of the oxygen evolution reaction on Ti/IrO2 electrodes using isotope labeling and online mass spectrometry. Electrochem Commun 9:19691974 (2007). 4 Foti G, Gandini D, Comninellis C, Perret A and Haenni W, Oxidation of organics by intermediates of water discharge on IrO2 and synthetic diamond anodes. Electrochem Solid State Lett 2:228230 (1999). 5 Marselli B, Garcia-Gomez J, Michaud PA, Rodrigo MA and Comninellis C, Electrogeneration of hydroxyl radicals on boron-doped diamond electrodes. J Electrochem Soc 150:7983 (2003).

6 Panizza M, Michaud PA, Cerisola G and Comninellis C, Anodic oxidation of 2-naphthol at boron-doped diamond electrodes. J Electroanal Chem 507:206214 (2001). 7 Thompson TL and Yates JT, Surface science studies of the photoactivation of TiO2 new photochemical processes. Chem Rev 106:44284453 (2006). 8 Berberidou C, Poulios I, Xekoukoulotakis NP and Mantzavinos D, Sonolytic, photocatalytic and sonophotocatalytic degradation of malachite green in aqueous solutions. Appl Catal B 74:6372 (2007). 9 Kaur S and Singh V, Visible light induced sonophotocatalytic degradation of Reactive Red dye 198 using dye sensitized TiO2 . Ultrason Sonochem 14:531537 (2007). 10 Canizares P, Martnez L, Paz R, S ez C, Lobato J and a Rodrigo MA, Treatment of Fenton-refractory olive oil mill wastes by electrochemical oxidation with boron-doped diamond anodes. J Chem Technol Biotechnol 81:13311337 (2006). 11 Khare UK, Bose P and Vankar PS, Impact of ozonation on subsequent treatment of azo dye solutions. J Chem Technol Biotechnol 82:10121022 (2007). 12 Mantzavinos D and Psillakis E, Enhancement of biodegradability of industrial wastewaters by chemical oxidation pretreatment. J Chem Technol Biotechnol 79:431454 (2004). 13 Carey JH, Laurence J and Tosine HM, Photodechlorination of PCBs in the presence of titanium dioxide in aqueous suspensions. Bull Environ Contam Toxicol 16:697701 (1976). 14 Malato S, Blanco J, Alarcon DC, Maldonado MI, Fern ndeza Ib nez P and Gernjak W, Photocatalytic decontamination a and disinfection of water with solar collectors. Catal Today 122:137149 (2007). 15 Blanco-G lvez J, Fern ndez-Ib nez P and Malato-Rodrguez S, a a a Solar photocatalytic detoxication and disinfection of water: recent overview. J Solar Energy Eng 129:415 (2007). 16 Malato S, Blanco J, Maldonado MI, Oller I, Gernjak W and P rez-Estrada L, Coupling solar photo-Fenton and biotreate ment at industrial scale: main results of a demonstration plant. J Hazard Mater 146:440446 (2007). 17 Gogate PR and Pandit AB, A review of comparative technologies for wastewater treatment. I: Oxidation technologies at ambient conditions. Adv Environ Res 8:501551 (2004). 18 Kamp PC, Martijn BJ and Kruithof JC, Removal of organic micropollutants with UV/H2 O2 . IWA Leading Edge Technology Conf, Singapore, pp. 000000 (2007). 19 Esplugas S, Bila DM, Krause LGT and Dezotti M, Ozonation and advanced oxidation technologies to remove endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) in water efuents. J Hazard Mater 149:631642 (2007). 20 Belgiorno V, Rizzo L, Fatta D, della Rocca C, Lofrano G, Nikolaou A, et al, Review on endocrine disrupting-emerging compounds in urban wastewater: occurrence and removal by photocatalysis and ultrasonic irradiation for wastewater reuse. Desalination 215:166176 (2007). 21 Pauwels B, Deconinck S and Verstraete W, Electrolytic removal of 17-ethinylestradiol (EE2) in water streams. J Chem Technol Biotechnol 81:13381343 (2006). 22 Paspaltsis I, Kotta K, Lagoudaki R, Grigoriadis N, Poulios I and Sklaviadis T, Titanium dioxide photocatalytic inactivation of prions. J Gen Virol 87:31253130 (2006).

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J Chem Technol Biotechnol 83:769776 (2008) DOI: 10.1002/jctb