Phytoremediation Technologies

Subject Area 5.3

Subject Area 5.3: Phytoremediation and ecosystem restoration

Discussion Article

Using Phytoremediation Technologies to Upgrade Waste Water Treatment in Europe

Peter Schrder1*, Juan Navarro-Avi2, Hassan Azaizeh3, Avi Golan Goldhirsh4, Simona DiGregorio5, Tamas Komives6, Gnter Langergraber7, Anton Lenz8, Elena Maestri9, Abdul R. Memon10, Alfonso Ranalli11, Luca Sebastiani12, Stanislav Smrcek13, Tomas Vanek14, Stephane Vuilleumier15, Frieder Wissing16
Department of Microbe-Plant Interactions, GSF National Research Center for Environment and Health, Neuherberg, Germany Department of Stress Biology, Polytechnical University of Valencia, Spain 3 R&D Center the Galilee Society, Shefa-Amr, Israel 4 The Jacob Blaustein Institutes for Desert Research, Ben Gurion University of the Negev, Israel 5 Faculty of Mathematics, Physics and Natural Sciences, Department of Biology, Pisa, Italy 6 Plant Protection Institute, Hungarian Academy of Sciences, Budapest, Hungary 7 Institute of Sanitary Engineering and Water Pollution Control, BOKU-University of Natural Resources and Applied Life Sciences, Vienna, Austria 8 Ingenieurbro Lenz, Ringelai, Germany 9 Department of Environmental Sciences, University of Parma, Italy 10 TUBITAK Research Institute for Genetic Engineering and Biotechnology, Gebze, Turkey 11 Istituto Sperimentale de l`Elaiotechnica, CNR, Pescara, Italy 12 Scuola Superiore di Studi Universitari e di Perfezionamento Sant'Anna, Pisa, Italy 13 Analytical Chemistry Laboratory, Charles University, Prague, Czech Republic 14 Department of Plant Cell Tissue Cultures, Czech Academy of Sciences, Prague, Czech Republic 15 Department Microorganisms, Genomes, Environnement, UMR 7156 CNRS, Universit Louis Pasteur Strasbourg, France 16 ILKON Engineering Office for Applied Limnology, Bonn, Germany
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* Corresponding author: Prof. Dr. Peter Schrder, GSF National Research Center for Environment and Health, Department of Microbe-Plant Interactions, Ingolstdter Landstrasse 1, 85764 Neuherberg, Germany (peter.schroeder@gsf.de)
DOI: http://dx.doi.org/10.1065/espr2006.12.373
Please cite this paper as: Schrder P, Navarro-Avi J, Azaizeh H, Goldhirsh AG, DiGregorio S, Komives T, Langergraber G, Lenz A, Maestri E, Memon AR, Ranalli A, Sebastiani L, Smrcek S, Vanek T, Vuilleumier S, Wissing F (2007): Using Phytoremediation Technologies to Upgrade Waste Water Treatment in Europe. Env Sci Pollut Res 14 (7) 490497

Abstract Goal, Scope and Background. One of the burning problems of our industrial society is the high consumption of water and the high demand for clean drinking water. Numerous approaches have been taken to reduce water consumption, but in the long run it seems only possible to recycle waste water into high quality water. It seems timely to discuss alternative water remediation technologies that are fit for industrial as well as less developed countries to ensure a high quality of drinking water throughout Europe. Main Features. The present paper discusses a range of phytoremediation technologies to be applied in a modular approach to integrate and improve the performance of existing wastewater treatment, especially towards the emerging micro pollutants, i.e. organic chemicals and pharmaceuticals. This topic is of global relevance for the EU. Results. Existing technologies for waste water treatment do not sufficiently address increasing pollution situation, especially with the growing use of organic pollutants in the private household and health sector. Although some crude chemical approaches exist, such as advanced oxidation steps, most waste water treatment plants will not be able to adopt them. The same is true for membrane technologies. Discussion. Incredible progress has been made during recent years, thus providing us with membranes of longevity and stability and, at the same time, high filtration capacity. However, these systems are expensive and delicate in operation, so that the majority of communities will not be able to afford them. Combinations of different

phytoremediation technologies seem to be most promising to solve this burning problem. Conclusions. To quantify the occurrence and the distribution of micropollutants, to evaluate their effects, and to prevent them from passing through wastewater collection and treatment systems into rivers, lakes and ground water bodies represents an urgent task for applied environmental sciences in the coming years. Recommendations. Public acceptance of green technologies is generally higher than that of industrial processes. The EU should stimulate research to upgrade existing waste water treatment by implementing phytoremediation modules and demonstrating their reliability to the public.
Keywords: Aquatic macrophytes; constructed wetlands; helophytes, personal care products; pharmaceuticals; phytoremediation; recalcitrant organic xenobiotics

Introduction

Today, more than 100,000 different chemicals are available on the European market, and one third of them exceed quantities of one tonne per annum. Most of them have been introduced for the benefit of daily life, medicine, food production and industrial purposes, and a good proportion of these compounds lack natural counterparts. The majority of these compounds have a rather poor biodegradability. Hence, fresh water resources become more and more contaminated with microquantities of these man-made pollutants. Moreover, some of these pollutants may possess the undesirable property of exerting estrogenic activity on various higher organisms. Europe has to face the issue that many of these foreign compounds or

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xenobiotics will increasingly create environmental problems in all regions of our continent. Due to steadily improving capabilities for environmental analysis, we are nowadays able to detect compounds in very low concentration ranges (e.g. nanomoles) in water bodies and sediments. Amongst them are well-known pesticides, plasticizers, fuel additives, flame retardants, medicaments and fragrances. Industrial activities are a second source of water pollution. Industrial wastewater discharged into aquatic ecosystems either directly or because of inadequate treatment of process water can lower water quality of a region by increasing concentrations of pollutants such as organic matter, suspended particulates, micropollutants, nutrients (phosphorus and nitrogen) or heavy metals, thereby causing adverse effects on human health and undesirable changes in the composition of aquatic biota. It becomes increasingly clear that societal attitude towards water pollution is associated with rising economic costs because of the ensuing depletion of water resources for specific uses. The reduction of pollution in waste water will depend on what a given community or an industrial area allows into the effluent stream, and on the efficiency and effectiveness with which these effluents are treated. The special treatment requirements for industrial effluents differ from those of municipal wastewater. In case of industrial effluents, where specific pollutants are well defined, targeted treatment at source can be applied. Municipal waste water treatment may require more diverse technologies. The ETAP (Environmental Technologies Action Plan) of the European Union claims urgent action for better water quality and protection of our natural resources. High priority is also given to environmentally sound water treatment technologies that will reduce greenhouse gases, recycle materials and provide all partner countries with affordable technologies. The discussion paper on water issues is very specific about novel green technologies to be adopted in this respect (http://europa.eu.int/comm/environment/etap/pdfs/etapwater issuefr.pdf). Hence, it would be timely to target on new, environmentally benign, biological technologies for the removal of toxic pollutants from water. This will have the additional beneficial effects of a reduced health risk to people and ecosystems, and will exploit available research excellence by collaboration with industry. Better environmental conditions as a result of reduced impact of pollution discharges in European countries will also create favorable conditions for social development and for overall industrial activity. The EU Strategy for Sustainable Development (European Commission 2004) and several EU directives strive to provide Europe with clean water of high purity and stable quality. This addresses all types of water use, but especially considers drinking water. Conventional waste water treatment systems have not provided adequate solutions for the removal of micropollutants, especially pharmaceuticals, personal health products and heavy metals. Although high-tech solutions are presently available all over Europe, their sustainability is usually not achieved, since their resilience to numerous parameters is questionable, and clear cut evidence is presented in the ETAP papers that these technical solutions are too expensive for many communities. It is also evident that, in order to protect resources for future

Phytoremediation Technologies
generations, approaches have to be adopted which will not only preserve the ecosystem, but also protect biodiversity.
1 Micropollutants in Urban Waste Water and Sludge

Pharmaceuticals have been detected in surface waters of the US and Europe at concentrations in the ng/L to g/L range (Kolpin et al. 2002). A German study reported on the occurrence of 55 active pharmaceuticals and 9 metabolites in the discharge of 49 sewage treatment plants, as well as in receiving water bodies, at concentrations of up to several g l1 (Ternes 1998). Another study reports that 27 out of 32 pharmaceutical substances and 4 of 5 metabolites were detected in the effluent of European wastewater treatment plants, and that surface water peak values exceeded 1 g l1 (Larsen et al. 2004). American studies came up with similar values, and pointed out that numerous compounds found in sewage plants will consequently also be present in potable-water supplies and, hence, represent a public health problem of increasing concern (Stackelberg et al. 2004). In other cases, municipal waste water treatment plants may receive considerable amounts of pre-treated industrial waste water, polluted ground water, etc., leading to additional pollution with organic xenobiotics. Reviews on the occurrence, fate and possible effects of pharmaceuticals or their active metabolites in the environment from sewage and animal husbandry are available and point to the danger of their widespread distribution in ecosystems (Daughton and Ternes 1999, Sweetman 2002). Few recent papers describe also the occurrence of perfluorinated surfactants in water (Skutlarek et al. 2006). However, the environmental effects of the presence of many other compounds and mixtures thereof in waste water have not been properly addressed with respect to their biological activity (Richardson and Bowron 1985, HallingSorensen et al. 1998, Daughton 2001, Ternes 2001). A second problem arises when surplus wastewater sludge is reused as a fertilizer for agricultural purposes. This sludge must clearly conform to certain limit values with respect to xenobiotic substances in order to prevent accumulation in soil, plant and drainage to surface and ground water. The latest revision of the statutory order in Denmark, for the first time, included a list of limit values on organic micropollutants in sludge. Four groups of micropollutants were included in this list: the Linear Alkylbenzene Sulfonates (LAS), Polycyclic Aromatic Hydrocarbons (PAH), Nonylphenols + Ethoxylates (NPE), and Diethylhexyl-Phthalates (DEHP) (Knudsen et al. 2000). The fate of pharmaceuticals or personal care products in sludge is rarely addressed. Today, up to 50% of the sludge used for agricultural purposes does not comply with the given standards. Nevertheless, this sludge is used as an amendment to soils and, hence, delivers organic pollutants to soil, surface water and crops. It has been observed that the level of organic micropollutants is much higher in anaerobically digested sludge than in aerobically stabilized sludge. This indicates that the organic micropollutants in question can be degraded at least in part under aerobic conditions, but not under anaerobic conditions. These observations suggest an attractive starting point for the development of a post-aeration process for biological degradation of organic micropollutants in anaerobically digested sludge with the aim of enabling continued reuse of the sludge for agricultural purposes.

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trients has already resulted in a significant improvement in the quality of the receiving waters. However, none of the emerging organic micropollutants (e.g. pharmaceuticals, personal care compounds, endocrine disrupting substances) is targeted by conventional treatment plant design. Kreuzinger et al. (2005) describe an approach to determine comparable removal rates of endocrine disruptors (EDs) and pharmaceutically active compounds (PhACs) for different activated sludge systems, based on mass balance and sludge retention time, in order to allow comparison and evaluation of the removal efficiency of different layouts and concepts in wastewater treatment. Presented results from different WWTPs (waste water treatment plants) show a close correlation of removal of EDs and PhACs to the sludge retention time. However, this experience has not been taken into account into design guidelines up to now. Hence, another important issue concerns the treatment plant size. Directive 91/271/EEC only focuses on larger treatment units, i.e. facilities for more than 2,000 people. However, a vast majority of WWTPs is of a very small size. In other words, most single treatment plants, taken alone, contribute only very little to environmental pollution. However, the large total number of small WWTPs in operation results in a big overall burden to the environment. Here, solutions that will be adaptable for different scales, from the very small units to significant sizes of 10,000 to 50,000 person units, should therefore represent a major objective in contemporary plant design. State-of-the art WWTPs combine physical, chemical and biological treatment steps to remove solids and nutrients, perform flocculation and sedimentation, and precipitate phosphates to reduce the danger of eutrophication of surface waters. Eighty percent of European waste waters pass through such a treatment plant before they are discharged into the environment (O'Brien and Dietrich 2004). Conventional sewage treatment plants throughout Europe adopt a system of 3 different steps, a primary clarifier, an activated sludge basin, and a secondary clarifier (Fig. 1). In the pri-

International Conventions and Agreements

Since the North Sea Conference on Co-operation in dealing with pollution of the North Sea by oil and other harmful substances (Bonn Agreement 1983), public awareness in Europe has been introduced to the topic of water quality. Still, it took almost a decade until the Hague Declaration on the future Community ground water policy was agreed on at the EC Ministerial Meeting on Nov. 2627, 1991. Another decade went by until the Agenda 21 formulated the idea that quantitative and qualitative discharge standards for municipal and industrial effluents should be established and applied by the year 2000. Connected to this recommendation was the proposal to revise Directive 76/464/EEC (Dangerous Substances in Water) and the Directive No. 96/ 61 EC on Integrated Pollution Prevention and Control (IPPC 1996), as well as Directive 93/793/EEC on environmental risk from chemicals (testing the ecotoxicity of listed priority chemicals). Updated European framework legislation promotes the reduction of micropollutants. Substantial political concern exists that water pollutants have to be monitored and removed. However, our knowledge of xenobiotics control or degradation has hardly gone beyond scratching the surface and confirming the importance of the problem. In particular, it is not known to which extent the treatment of waste water in a municipal waste water treatment plant is feasible with regard to environmental effects and costs.
3 Operation of Wastewater Treatment: Current state of the Art

The state-of-the-art in the design of wastewater treatment plants has been improved steadily since the middle of the last century. Their performance is strongly related to the relevant legal framework, i.e. the compounds for which effluent standards are relevant. According to the EU Urban Wastewater Directive 91/271/EEC, the relevant parameters for design are organic matter (expressed as BOD5, COD and TOC) and nutrients like nitrogen and phosphorous (albeit only in sensitive areas). The increased removal of organic matter and nu-

Activated sludge tank

Secondary clarifier

anaerobic

anoxic

nitrification

Effluent containing micropollutants

Fig. 1: State of the art of wastewater treatment (modified after Siegrist et al. 2004). From left to right: Primary clarifier for sedimentation of solids; Activated sludge basin for microbial decomposition of nutrients and pollutants; Secondary clarifier for removal of fines and chemicals by absorption processes. Sludges from clarifiers and from the activated sludge system are treated separately and finally disposed

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mary clarifier, suspended solids are sedimented and build up a first sludge fraction. In the activated sludge basin, nutrients and pollutants are in part decomposed by nitrification / denitrification, biological mineralization, and stripping by aeration. Furthermore, phosphate is retained by polyphosphate-accumulating bacteria. The secondary clarifier removes fines and chemicals by absorption processes based on hydrophobic interactions, or by adsorption due to electrostatic interactions of positively charged groups of chemicals with the negatively charged surfaces of microorganisms. Sludge from the primary clarifier and the surplus sludge from the activated sludge system are treated in separate units and finally disposed (Siegrist et al. 2004). Despite these developments, wastewater treatment does not comply with the same standards throughout the EU. The diverse technological standards existing in different countries of the EU aside, legislation of individual countries has addressed pollution reduction in different ways. Furthermore, factors governing the selection of municipal and industrial wastewater treatment technologies are today subject to major changes: Increasing expectations in European society for clean water and a healthy environment are now manifested in stricter EU legislation and control. This clearly calls for new developments in advanced treatment technologies and is a unique opportunity to bring new and 'green' processes into focus. The removal of micropollutants and potential applications of novel membrane techniques (e.g. Clara et al. 2005) are amongst the aspects of wastewater treatment that generate the greatest interest at present. Due to their relatively high costs and maintenance requirements, they will, however, only be adopted in larger WWTPs of wealthier communities.
4 Ongoing Research Activities in EU-Funded Programs

Phytoremediation Technologies
retention of problem compounds in the sludge or the biotic compartment of wastewater treatment plants. Moreover, most sewage treatment plants release more than the originally proposed effluent to surface water in a ratio of 1:10 into accepting water bodies. Hence, as promising as these technologies might be, they do either require an incredibly high standard of wastewater pretreatment, inadequately low throughputs, or high input of energy and resources. Ozonation would, for example, guarantee a 90% reduction of micropollutants in sewage treatment plants, although the costs of the installation and of the operation make this system unattractive for most communities. Urine separation, on the other hand, would require a complete alteration in the sewage system of a community. This seems unrealistic. All presently available technologies have failed to alleviate the load of pollutants from our waters. Treatment facilities across Europe urgently need upgrading to fulfill recently upgraded water standards, and to keep the end-users healthy. With view to the ongoing enlargement of the EU, sound technologies would have to be developed that are sustainable and affordable for border countries and adaptable to existing treatment technologies.
5 Upcoming Solutions

As the concern about water pollution has reached a European Dimension, the EU has fostered research on the topic of water treatment during FP5 and FP6. So far, research on conventional sewage treatment, on advanced oxidation procedures, and on membrane technologies have been financed. Successful projects deliver important data to the EU, which can be retrieved at several websites. Some examples are given here:
http://here.alfalaval.com/ http://www.aquabase.com http://www.europa.int/comm/research/endocrine/pdf/env4-ct980798.pdf http://www.cranfield.ac.uk/ecochemistry/eravmis http://www.cdcs.unina.it/-rmarotta http://edenresearch.info http://www.eu-poseidon.com http://www.iwaponline.com/wio/2002/03/wio200203021.htm

Across Europe, with its climatic gradients, specific pollutant situations and demands for a supply of clean water, an integration of technologies will be needed. Research has to begin at end-of pipe-problems, i.e. at the effluent tubes of sewage treatment plants currently in operation. Here, mixtures of recalcitrant pollutants occur in relatively clean water. In such an oligotrophic system, a potent microflora capable of degrading stable pollutants can only exist when nutrients are added. Amendments of carbon and nitrogen sources can, of course, be made use of by adding mineral fertilizer to the system. A much more elegant way to supply the microflora can be reached by plant canopies in artificial wetlands. Furthermore, if plants with high transpiration rates are selected in such a canopy, they will be able to take organic micropollutants up and distribute them in their tissues, where further metabolism will occur (Coleman et al. 2001, Schrder 1997, 2001, 2003, 2004, Schrder and Collins 2003, Schrder et al. 2005, Golan-Goldhirsh et al. 2004). This is also true for sludge treatment and drying by reed beds, as applied in Denmark (Nielsen 2003, 2005). It is obvious that such plant-microbe associations will have to be designed specifically for specific environmental conditions, and for the specific pollution / climate interactions of the region of interest. Compared to engineering-based technological approaches, these green bioremediation (phytoremediation) techniques currently being developed and applied in constructed wetlands and barrier systems seem rather poor. However, they have been demonstrated to be very effective in numerous cases and especially in small systems, although they might appear somewhat primitive. Especially in small systems, they will guarantee a stable effluent quality with low nutrient content, thus affording high hygienic levels (Vanek and

These projects and organizations have achieved significant progress in wastewater treatment, and their results on micropollutants indicate removal rates in the range of 70 to 90% (O'Brian and Dietrich 2004). Especially approaches with membrane technologies, ozonation or with urine separation technologies (http://www.novaquatis.eawag.ch) seem promising with respect to high effluent quality. One of the reasons for the residual pollution load in effluents seems to be the short residence time in the system and the inadequate

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Phytoremediation Technologies
Schwitzguebel 2003). Several techniques can be distinguished amongst phytoremediation technologies: phyto-extraction, phyto-degradation, phyto-volatilization; rhizosphere degradation, and constructed wetlands (Schrder and Hartmann 2003). The green technologies proposed in the following paragraphs have several key features in common; they are of high sustainability, require a low input in energy and manpower, and offer possibilities of carbon sequestration in biomass, as well as the recycling of materials and matter. Constructed wetlands. Conventional treatment systems that are based on submerged biomass are not as robust regarding shock loads compared to near-natural treatment systems, such as constructed wetlands (CWs). CWs are (semi-)artificial wetlands designed to improve water quality. They are effective in treating organic matter, nutrients and pathogens and are used worldwide to treat different qualities of water. Compared to conventional technical solutions for water treatment, CWs are relatively easy to maintain and to operate, resulting in low operating costs (Kadlec et al. 2000, Langergraber and Haberl 2001, Haberl et al. 2003, Langergraber and Haberl 2004). The pioneering work of COST action 837 has led to the identification of the most promising helophytes for constructed wetlands, amongst them Phragmites, Typha and Brassica species, but also fast growing trees (lbewww.epfl.ch/COST837). Already through the use of simple horizontal flow CWs, the pollution load can be reduced significantly due to their high efficiencies for pollutant removal (e.g. Kadlec et al. 2000). The very low energy requirement of CWs (Brix 1999) saves energy resources. CWs perform quite favorably with other treatment technologies according to their sustainability in a life-cycle assessment (Dixon et al. 2003, Steer et al. 2003). Besides water quality improvement and energy savings, CWs have other features related to the environmental protection such as promoting biodiversity, providing habitat for wetland organisms and wildlife (e.g. birds and reptiles in large systems), and serving climatic (e.g. less CO2 production, Dixon et al. 2003) and hydrological functions (Brix 1999) and heavy metal bioaccumulation and biomethylation (Azaizeh et al. 1997, 2003). CW technology is emerging rapidly, and drawbacks will probably be minimized during further development. Vertical flow beds. The behavior in the environment of selected organic compounds and emerging organic micropollutants has been widely researched in the context of conventional water treatment during the last years (e.g. Bursch et al. 2004, Chaudry et al. 2001, Frhacker et al. 2003a, 2003b, 2004, Lenz et al. 2005a, 2005b, Mahnik et al. 2004). CWs have clearly been shown to be effective in treating wastewaters containing a large number of organic compounds (Haberl et al. 2003). Only recently, the first pioneering studies on the behavior of organic micropollutants in the context of CWs have been published (e.g. Kstner et al. 2003, Masi et al. 2004, Matamoros et al. 2005). These studies show that CWs are generally amenable to remove organic micropollutants such as endocrine disrupting chemicals, as well as pharmaceuticals and personal care products (PPCPs), but the degradation of the pollutants depends strongly on the chemistry within the rhizosphere and the

Subject Area 5.3

retention time in the CW. Here, the use of twin-shaped, constructed wetlands consisting of one or more vertical flow chamber and reverse vertical flow chambers seems to offer the highest removal efficiencies of xenobiotics from polluted water (Cheng et al. 2002, Schrder et al. 2005a). In connection with selected plant species that improve the oxygen supply to the rhizosphere, these systems offer habitats for rhizobacteria with different requirements and capabilities of pollutant degradation. Furthermore, they allow for intense contact of the pollutant with the root surfaces. Hydroponics. Being characterized by their extraordinary root growth, several helophytes can also be grown in hydroponic systems without soil. Such specific CWs might be useful when interactions between pollutants and the soil matrix have to be excluded due to pollutant chemistry (e.g. high log Kow), or when the plant material as a whole has to be harvested and removed after the pollutant has been accumulated in the tissue. Specifically Phragmites, Iris, Juncus, but also Menyanthes and Panicum seem to form extensive reeds under such growth conditions (Wissing 2003). To stabilize the plant canopy, porous rubber or woven plastic mats can be used to provide support and shelter to the growing roots. Periodical aeration seems to stimulate root growth and biomass development. Hydroponic systems underpin the role of the plant and its metabolism for the uptake and degradation of the pollutant under consideration. They are highly sustainable, and might also contribute to diminishing greenhouse gas emissions (Dixon et al 2003). Hybrid systems. Depending on the possibilities of the WWTP and its demands, it might be useful to add phytoremediation modules that are mixtures of the above examples. Novel ideas might be the operation of flooded horizontal beds with floating species (Eichhornia, Pistia, Lemna), or the inclusion of helophytes or terrestrial plant species with different rooting depths in vertical flow beds. Root surface chemistry and aeration of roots might also be of concern, and have so far not been studied with respect to rhizofiltration. Mixed stands of plants will generally be more stress resistant than monocultures, and establish a higher diversity of rhizobacteria. Furthermore, the combination of plants able to degrade specific pollutants will increase the efficiency. For example, Phragmites seem to be a good candidate for the removal of pesticides (Schrder et al. 2005b), but it will be subject of further studies to test its ability to degrade pharmaceuticals. Successful remediation of pollutants has also been demonstrated in flooded soil systems planted with trees. Here, the plant's role might be confined to the support of rhizosphere bacteria, the evaporation of excess water and the potential volatilization of pollutant metabolites. Several wetland trees (poplar, birch, willow) and other plant species have been described to have a good potential for rhizostabilization of pollutants for further microbial degradation and treatment of the sludge. Also the volatilization of xenobiotics has been demonstrated as a possible way to diminish the pollutant burden in the water body (Burken and Schnoor 1999, Ma and Burken 2003). In any case, the selection of suitable soil/sediment systems and residence times seems crucial for the operation in a WWTP and has to be tested thoroughly.

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Fenton's Oxidation. Another set of novel but chemistry-based approaches involves advanced oxidation techniques (AOP) relying on the generation of hydroxyl radicals through various techniques, such as vacuum-UV radiation (V-UVR), electrochemical oxidation, use of ozone and/or hydrogen peroxide in combination with UV-radiation (Lenz et al. 2005a). The reactivity of metals and hydrogen peroxide to yield highly reactive hydroxyl radicals was first reported by Fenton in the late nineteenth century. In the presence of a metal catalyst (usually iron(II) chloride or sulphate), a hydrogen peroxide solution forms hydroxyl radicals (OH). The mechanism was studied in detail by Haber-Weiss and it is referred to as the Haber-Weiss reaction, where super oxide ion and hydrogen peroxide (often in the presence of Fe(III) as catalyst) react to yield a hydroxyl radical, oxygen and a hydroxyl ion. They can oxidize most organic substances into CO2 and H2O. If there are not enough radicals, organic compounds are decomposed to lower organic acids. Addition of a reducing agent, such as ascorbate, leads to a cycle (HaberWeiss cycle) which increases damage to organic and biological molecules. It was shown that copper and ascorbic acid can preferentially break down histidine in proteins in a Haber-Weiss type reaction (Shinar et al. 1983, Golan-Goldhirsh et al. 1992), which opens a potential for a more targeted approach in organic compound breakdown based on this reaction. In the use of this reaction in the context of wastewater treatment, organic substances would decomposed in a separate WWTP-module by mixing waste water with hydrogen peroxide and an iron catalyst, before the waste water is neutralized. As a practical advantage, the iron catalyst precipitates as iron hydroxide. Fenton's reagent can be applied in a batch or continuous process and guarantee degradation of residual pollutants.
6 The European Dimension: Objectives and needs for the future

Phytoremediation Technologies
tion, or the Fenton reaction in existing wastewater treatment facilities, it will be necessary to study in more detail the prevailing interactions between pollutants and the plant/ bacterial consortia in this context. We propose evaluating such novel treatment modules by grafting them onto existing sewage treatment facilities of different types (Fig. 2), and also along a climatic gradient from humid north European through Mediterranean to harsh desert climates, in order to gain an insight into the underlying biochemistry and biology, and to evaluate the resulting effluent quality. This will allow us to gain a better understanding and evaluation of the specific needs of different types of treatment plants in different geographical situations, and to better implement cost-efficient, tailor-made adjustments to specific pollution problems on a case by case basis. Only thorough testing of phytoremediation technologies will enable the EU to set regional conditions for stable effluent quality and consumer security, in concert with high sustainability.
7 Perspectives

The main aim of applied environmental sciences in the field of wastewater treatment has to be the amelioration of the effluent quality from WWTPs and the enforcement of reliable standards of regenerated waters in contact with ground water resources. Only hereby will Europe be able to increase the sustainability of drinking water resources and contribute in a modest way to decrease effects of global change by lowering energy usage, CO2 emission and waste production during wastewater treatment. It will be necessary to demonstrate cost effectiveness, reliability, long-term sustainability, resilience and reasonable input of resources, especially for border countries, before local decision-makers can accept such a change in the water treatment procedure for their region. Contrary to most technical solutions, the implementation of phytoremediation would address these demands. Here, cost effectiveness is achieved by recycling, using energy saving biological processes, and by producing biomass, potentially biologically active compounds for medicinal use, and other non-food products for energy production, green manure and building materials. Furthermore, constructed wetlands are low-cost maintenance systems. Compared to traditional sewage treatment methods, it can be stated that 'green technologies' are more appropriate for water clean up for the following reasons: they decompose organic pollutants to non-toxic low molecular substances easily degraded by microorganisms, they do not introduce additional chemical substances into the environment (solvents, alkali, PEG), they are relatively easy to manage and they can be easily adopted to the local needs, they do not require large investment to be practically introduced, they are able to remove several pollutants in combination, they can be applied at a small as well as at a large scale. Of special importance is their functionality in a modular design, i.e. relatively small containments that would be coupled to existing WWTPs corresponding to the specific day-to-day requirements of changing wastewater qualities. Such systems will be reliable because the functioning of the

Directive 91/271/EEC on urban wastewater treatment and Directive 96/61/EC on Integrated Pollution Prevention Control illustrate the current and future EU policy to encourage development of processes and standards to prevent negative effects on water, using best available technologies. The limiting biodegradative capacity of natural microbial associations necessitates the development of more integrated water treatment and management. Research is needed (1) to search for biotechnological processes capable of removing such chemicals through engineering of biochemical pathways in plants and microbial associations, and (2) to find reliable biosensors able to generate information on residual micropollutants. Recent trends to exploit improved plant canopies and for accurate process control are of major significance in this context. However, clear-cut scientific and political endorsement of the necessity to use reclaimed wastewater is of prime importance for evolving more sustainable water management. Protection of the quality and supply of freshwater, thus, needs integrated approaches to the development, management and protection of water resources. The European wastewater problem will have to be tackled soon, since the mentioned EU directives require urgent action. In order to recommend currently promising technologies such as phytoremediation, ozonation, membrane filtraEnv Sci Pollut Res 14 (7) 2007

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Activated sludge tank Secondary clarifier

anaerobic

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Effluent containing micropollutants

Test y/n

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Optional phytoremediation and AOP modules

Fig. 2: Optimizing existing waste water treatment plants. Innovative green or AOP technologies are used to upgrade existing wastewater treatment plants that have increasing problems of removing recalcitrant micropollutants. The additional modules (e.g. oxygenation, constructed wetlands, aquatic macrophytes, hydroponics/reed beds, swamp system with trees, hybrid systems with mixed stands, AOP) are introduced facultatively into the system. Thorough testing for water quality is performed after each module to ensure water quality standards. Polluted water is retained or pumped back into the module

single modules has been demonstrated in several existing pilot studies. A combination of these eco-techniques is a novel approach that will further improve the reliability. Long-term sustainability is achieved by integration of biological processes and the use of environmentally friendly materials and agents to the process. Hence, such systems will operate with reasonable input of resources, as they represent microcosms that stabilize themselves. Plant harvest, maintenance, and de-clogging are low input activities that require no specifically educated personnel. Public acceptance of green technologies is generally higher than that of industrial processes. The expected, excellent water quality will lead to additional consumer satisfaction, sustainability for future generations, contribute to recreation and ecoesthetics, and it will contribute to the protection of the vulnerable parts of society, women, children, and the elderly, from pharmaceuticals and dangerous micropollutants.
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