Whether or not there will be a phosphorus (P) peak within decades, centuries or millennia, (Cordell and White, 2011; Scholz and Wellmer, 2013) one thing is for sure – phosphorus is a limited and, in its function as a nutrient, an essential and irreplaceable resource (Asimov, 1959; Smil, 2000; Filippelli, 2008). The debate on P limitation is often mentioned as motivation to foster activities regarding P recovery and recycling. The ambition of the European Commission (EC) to establish a circular economy in Europe goes far beyond that and is not primarily motivated by limitations of certain raw materials. From the European perspective and in the light of having just one small mine in Finland, the geopolitics and economic vulnerability are issues to be taken seriously. Europe is highly dependent on phosphorus imports (De Ridder et al., 2012) as reflected by the quantities given in figure 1. In contrast to the above mentioned issues, the waste and dissipation of phosphorus that exists in developed countries may lead to a different conclusion. The global resource efficiency for P along the supply chain from mine to fork is only 20% (Schröder et al., 2010). Given the figures of 225 million tons P rock globally mined in 2013 (USGS, 2015) and assuming that 90% of the mined P is used for food production, only 45 million tons of the mined quantity finally ends up in form of food on our tables. So, what can we do to increase the resource efficiency of P? Recently, the implementation of a coherent package of nutrient management strategies and measures to close the European P cycle has been proposed – the 5R strategy (Withers et al., 2015). The five R’s are Realign P inputs, Reduce P losses to waters, Recycle P in bio-resources, Recover P from waste and finally Redefine our food system. So, recovery and recycling can play an important role in improving resource efficiency and sustainable nutrient management. Although, there are various relevant waste streams carrying huge quantities of phosphorus dissolved in liquids or fixed in solids like in manure or organic waste, the focus of P-REX was laid upon P recovery and recycling from wastewater and sewage sludge.

The La Vall d’Uixó (Spain) pilot site has been selected by DEMEAU because it is a new Aquifer Storage Transfer and Recovery (ASTR) site consisting of two injection wells surrounded by farmer wells for irrigation in a water scarce area. Potential water source for this MAR site is the effluent of the local WWTP, which is a quite constant water source in terms of availability, but gives concerns in terms of water quality. The investigations carried out within DEMEAU supports the work previously done by the Water Recovery Project (2011 – 2014), coordinated by IGME (Instituto Geológico y Minero de España) and UJI (Universitat Jaume I). The Water Recovery Project consists of different implementation phases and aimed to establish an appropriate MAR scheme with reclaimed wastewater to counteract salinity ingress in the coastal aquifer. In the third phase of the project two injection wells have recharged 310,000 m3 with water from the Belcaire River. To foster the implementation of the fourth and final phase of the Water Recovery Project, DEMEAU focused on the evaluation of the effluent of the local WWTP as source water for the ASTR system. This has been done by three sampling campaigns to analyse bulk chemistry, emerging pollutants and bioassays in native groundwater (six agricultural wells), Belcaire River (the current source water of the MAR scheme) and WWTP effluent (potential future source water). Risk assessment based on Australian MAR guidelines have been applied to evaluate risks related to the usage of WWTP effluent as source water. The Australian guidelines have been applied in two steps: entry level assessment and maximal risk assessment. Entry level assessment concluded that La Vall d’Uixó is suitable for a MAR scheme using reclaimed water, while maximal risk assessment identified hazards associated to reclaimed water as source water. As La Vall d’Uixó is an agricultural area of citrus crops, the use of reclaimed water for the injection in the MAR system must be compatible with the use of recovered water for irrigation. The risk assessment done in this report considered this end use of water, as there are no drinking water wells in the area. High risks have been identified for inorganic chemicals (conductivity, chloride and bicarbonate) and nutrients (nitrate). Risks associated to inorganics can be minimized by mixing effluent and Belcaire River water 1:1. Bulk chemistry coincided mainly with the description carried out in Water Recovery project, identifying two main quality problems in native groundwater: (1) salinity ingress (2) high nitrate concentration due to the intensive agricultural practices in the area. Ion displacement pattern in groundwater samples clearly indicates on-going salinization and documents minor effects of the injected water on few wells only. Cl/Br ratios indicate additional sources of chloride apart from seawater. It seems plausible that the underlying Keuper formations (Triassic) contribute to salinity ingress and SO4 excess in groundwater to some extent. Chlorides and nitrate are regulated by the implementation in Spain of the EU Water Framework Directive for the Castellón aquifer. The threshold value for nitrate is 200 mg/L, while the threshold value for chloride is 650 mg/L. WWTP effluent has nitrate and chlorides below the threshold concentrations (60 mg/L and 140 mg/L respectively) and, therefore, the MAR with reclaimed water would suppose a reduction of groundwater pollution and a step towards a qualitative good status in the aquifer. In total 63 organic micro pollutants have been analysed in groundwater, surface water and WWTP effluent. WWTP effluent shows elevated concentrations in almost all groups of organic micro pollutants compared to river- or groundwater. Only pesticides are found in higher concentrations in groundwater compared to the effluent. The Belcaire River shows the lowest concentrations for all groups of micro pollutants. It was shown that the Vall d’Uixó aquifer is contaminated by various organic micro pollutants and does not reflect a near natural aquifer condition. The aquifer chemistry in terms of organic micro pollutants reflects the usage of (untreated) effluent for direct irrigation over years. Elevated concentration of artificial sweeteners, analgesics, stimulants, caffeine metabolites and cocaine metabolites were found in WWTP samples taken during weekends compared to workday samples. In contrast, iopromide has been quantified in higher concentrations in the effluent of WWTP in work days than in the weekend, as this contrast media is used in hospitals for diagnostic tests normally carried out from Monday to Friday. These patterns of the effluent of WWTP during the week of weekend could be determinant for the selection of the working days as most suitable days to store treated waste water. In order to link analysed chemical concentrations to the observed toxicity in the samples a procedure based on bioassay-specific relative potency (REP) factors was applied. REP factors are determined by the effect concentrations of the reference compound and of the test compound. Despite the lack of toxicological data for a number of the selected target compounds and the lower relevance of the selected compounds for (eco)toxicological risk assessment, this study greatly demonstrate the usefulness of combined analyses of environmental samples. Effect-based methods could complement conventional chemical analysis in water quality monitoring as pre-screening techniques by (1) identifying toxic “hotspots” for further investigation, (2) assessing the effect of the entire mixture of compounds present in waters and therefore and (3) reduce uncertainty in safety evaluation.

The recovery of phosphorus (P) from sewage sludge, sludge liquor, or ash from monoincineration can be realized with different processes which have been developed, tested or already realized in full-scale in recent years. However, these pathways and processes differ in their amount of P that can be recovered in relation to the total P content in sludge, in the quality of the recovered P product, and in their efforts in energy, chemicals, fuels, and infrastructure required for P recovery. This study analyses selected processes for P recovery from sludge, liquor, or ash in their potential environmental impacts, following the method of Life Cycle Assessment (LCA, ISO 14040/44). Based on available process data from technology providers and end users, these processes are implemented in a hypothetical reference system for sludge digestion, dewatering and disposal in mono-incineration, including potential side-effects on mainstream wastewater treatment with the return load from sludge dewatering. Recovered products (e.g. P or N fertilizer, electricity, district heating) are accounted as credits for substituting equivalent industrial products. Depending on the maturity of the investigated process, collected process data of process efficiency, product quality, and energy and material demand originates from full-scale plants, pilot trials, or prospective modeling (status in 2014). This data is validated with the technology providers, transferred to the reference system and evaluated with a set of environmental indicators for energy demand, global warming, acidification, abiotic resource depletion, eutrophication, and human and ecotoxicity. Results show that pathways and processes for P recovery differ heavily in their amount of recovered P, but also in energy and related environmental impacts (e.g. greenhouse gas emissions). As direct struvite precipitation in sludge or liquor relies on the dissolved amount of P in digested sludge, these processes are only applicable in wastewater treatment plants with biological P removal. Here, they can recover 4-18% of total P in sludge with a relatively low effort in energy and chemicals, reducing return load to the mainstream process and eventually improving sludge dewaterability in case of direct precipitation in sludge. Acidic leaching of P from digested sludge can yield up to 48% of P for recovery, but requires a significant amount of chemicals for control of pH (leaching and precipitation) and for minimizing heavy metal transfer into the product. The quality of products from sludge and liquor is good with low content on heavy metals, leading to a low potential toxicity for humans and ecosystems. Leaching of monoincineration ash with sulphuric acid yields 70% P with moderate chemical demand, but the leached ash and co-precipitated materials have to be disposed, and the product contains some heavy metals. Complete digestion of ash in phosphoric acid and multi-stage cleaning with ion exchangers yields high recovery of 97% P in a high-quality product (H3PO4) and several coproducts, having an overall low environmental impact. Thermo-chemical treatment of ash can recover up to 98% P with moderate energy input in case of integration into an existing monoincineration facility, but the product still contains high amounts of selected heavy metals (Cu, Zn). Metallurgic treatment of dried sludge or ash can also recover up to 81% of P, but the process has still to be tested in continuous pilot trials to validate product quality, energy demand, and energy recovery options. Sensitivity analysis shows that other pathways of sludge disposal (e.g. co-incineration combined with upstream P extraction, direct application in agriculture) may also be reasonable from an environmental point of view depending on local boundary conditions and political targets. In general, the use of life-cycle based tools is strongly recommended to evaluate and select suitable strategies for regional or national concepts of P recovery from sewage sludge.

Im Rahmen des Projekte OgRe wurde das Ausmaß der Belastung von Regenablauf für Berlin durch ein einjähriges Monitoringprogramm in Regenwasserabfluss der Trennkanalisation unterschiedlicher Einzugsgebietstypen (Altbau, Neubau, Gewerbe, Einfamilienhäuser, Straßenablauf) untersucht. Ziel war, eine möglichst vollständige Erfassung organischer Spurenstoffe zu erreichen (einschließlich Identifizierung zusätzlicher Substanzen durch non-target-Analytik). Darüber hinaus sollte geklärt werden, inwieweit die unterschiedlichen Einzugsgebietstypen ein unterschiedliches Spektrum an Belastung durch Spurenstoffe aufweisen. Diese Informationen wurden dann genutzt, um eine Hochrechnung der über das Regenwasser in die Gewässer gelangenden Spurenstofffrachten für Gesamt-Berlin und einzelne Gewässerabschnitte zu ermöglichen. Die erhaltenen Frachten wurden verglichen mit modellierten Frachten abwasserbürtiger Spurenstoffe, die über Kläranlagenablauf in die Berliner Gewässer gelangen. Insgesamt wurden etwa 90 volumenproportionale Mischproben auf ein Set von etwa 100 Spurenstoffen analysiert. Zusätzlich wurden 12 Regenereignisse in der Panke beprobt, um Spitzenkonzentrationen regenwasserbürtiger Spurenstoffe im Gewässer zu ermitteln und ins Verhältnis zur Trockenwetterbelastung (5 Proben) zu setzen. Auch eine Untersuchung mikrobiologischer Parameter und der zeitlichen Dynamik konnten im Rahmen des Projektes durchgeführt werden.

This project report summarizes work conducted in work package 12 of the DEMEAU project. Along with Deliverable 12.1 it covers all tasks from work package 12 as formulated in the Description of Work (DoW). This report contains information about (pre-) feasibility studies, design recommendations and pre-treatment options for different types of MAR. The wide range of hydrogeological features encountered in reality makes a site-by-site approach indispensable. As part of this effort the hydrogeological pre-requisites for surface spreading and deep well injection techniques are described in detail. In chapter 2, ten essential hydrogeological parameters are defined by objective criterias. The following chapter outlines and describes how to obtain these essential hydrogeological parameters. This feasibility assessment starts with the screening of the potential site based on a structured procedure. Site investigations start with relatively cheap but numerous field and laboratory testing and continue to more cost-demanding but less numerous tests. With this procedure it is possible to carry out technical site feasibility in a costand time efficient way. The fourth chapter investigates the International Hydrogeological Map of Europe (IHME 1500) as a planning basis for pre-feasibility of new MAR sites. It was found that the IHME 1500 is useful for a pre-assessment, but detailed regional and local scale maps (and investigations) are additionally necessary to effectively assess hydrogeological features. The final chapter deals with pre-treatment options for MAR. Pre-treatment is necessary to remove critical contaminants from the source water to i) enhance system performance and removal efficiencies, ii) ensure the long-term functioning of the system, iii) meet regulatory demands and iv) ensure beneficial uses of the aquifer beyond the attenuation zone. Available pre-treatment methods in relation to source water type and intended end-use are described. Based on chemical concentrations in source water and intended end-use the most appropriate pre-treatment method can be assessed from a table. Altogether this report thus provides guidance in designing new MAR systems based on a sound hydrogeological site characterisation and pre-feasibility assessment based on available information and parameters obtained from structured investigations.

Die vorliegende wissenschaftliche Studie untersucht Potenziale und Grenzen der Hydrothermalen Karbonisierung (HTC) von entwässertem Klärschlamm zur Verbesserung der Energie- und Klimabilanz der Klärschlammentsorgung in Berlin. Für vier Berliner Klärwerke wurden Laborversuche zur HTC mit entwässertem Klärschlamm durchgeführt, um die Produkte HTC-Filtrat und hochentwässerter Klärschlamm zu charakterisieren. Mit diesen Daten und den Prozessangaben des HTC-Anbieters Terranova wurden Energieund Treibhausgasbilanzen für vier Klärwerke erstellt, die neben dem Referenzzustand 2013 für verschiedene Entsorgungswege auch die Implementierung eines HTC-Prozesses vorsehen. Abschließend wurde das HTC-Verfahren in einem technischen Pilotversuch mit zwei Berliner Klärschlämmen getestet und ebenfalls bilanziert. Die Laborversuche bestätigten die hohe Belastung des HTC-Filtrats mit CSB und N. Die organische Fracht im HTC-Filtrat zeigt im Biomethantest gute anaerobe Abbaubarkeit und einen entsprechenden Faulgasertrag. Der verbleibende CSB ist noch weiter aerob abbaubar (Zahn-Wellens-Test), so dass letztlich zwischen 1-14% der CSB-Fracht im Filtrat (7,4-14,5 g/L) als refraktär angesehen werden. Eine merkliche Rücklösung von Phoshor und Schwermetallen lässt sich erst bei stark sauren Bedingungen während der HTC (pH < 3) feststellen. Die Pilotversuche mit Klärschlamm aus Waßmannsdorf und Münchehofe in der Anlage des Anbieters Terranova konnten aufgrund von Problemen bei der Klärschlammaufgabe nicht kontinuierlich durchgeführt werden. Zudem wurde bei der abschließenden Entwässerung nicht der hohe prognostizierte TR-Gehalt im Klärschlamm erreicht (> 65% TR). Damit bleiben erhebliche Zweifel an der Betriebsstabilität und den prognostizierten Entwässerungsergebnissen bestehen. Die Energie- und Klimabilanz auf Basis der Labordaten und Herstellerangaben zeigt, dass die Einführung eines HTC-Prozesses für alle betrachteten Szenarien deutliche Vorteile bieten kann. Dabei spielt vor allem der erhöhte Faulgasertrag aus dem Prozesswasser (+16-19%) und der hohe Heizwert des hochentwässerten Klärschlamms eine Rolle. Die zusätzlichen Aufwendungen für den Prozess (Erdgas, Strom, Säure) und die höhere Rückbelastung des Klärwerks werden durch die Gutschriften ausgeglichen. Die Abwärme für den HTC-Prozess ist auf allen Klärwerken mit Faulung zu über 90% vorhanden, im Klärwerk Ruhleben sollte dazu eine separate Faulstufe für das HTC-Filtrat vorgesehen werden. Die Bilanzierung auf Basis der Daten aus den Pilotversuchen zeigt jedoch, dass die Vorteile der HTC deutlich geringer ausfallen, wenn Faulgasertrag im Filtrat und Entwässerbarkeit nicht erreicht werden. Der refraktäre CSB aus dem HTC-Filtrat kann im Ablauf der Klärwerke maximal zu einer Erhöhung des CSB-Ablaufwerts von 7-12 mg/L führen, was bei einzelnen Klärwerken eine Überschreitung der Überwachungswerte zur Folge haben kann. Dieser Aspekt ist bei der weiteren Betrachtung des HTC-Verfahrens unbedingt zu berücksichtigen. Eine Kombination von Phosphorrückgewinnung und HTC lässt sich über eine Rückgewinnung aus der Asche der Monoverbrennung oder eine vorgeschaltete P-Extraktion erreichen. Die abgeschätzten Betriebskosten der HTC-Anlage können ggf. durch Einsparungen bei der Schlammentsorgung ausgeglichen werden, wobei die Investitionskosten für eine HTC-Anlage noch unbekannt sind.

Der vorliegende Abschlussbericht fasst die Ergebnisse des Forschungsvorhabens IST4R (Integration der Spurenstoffentfernung in Technologieansätze der 4. Reinigungsstufe) zusammen, in dem verschiedene Verfahrenskombination von Aktivkohle und Ozonung zur Entfernung von anthropogenen Spurenstoffen als weitergehende Abwasserreinigung untersucht wurden. Dabei stand insbesondere die Integration dieser Verfahren in die Flockungsfiltration zur weitestgehenden Entfernung von Phosphor und abfiltrierbaren Stoffen im Fokus, die eine Planungsvariante zum zukünftigen Ausbau der Berliner Klärwerke darstellt. Ein wesentliches Ziel war die Bewertung der Verfahrensalternativen (1) Direktdosierung von Pulveraktivkohle, (2) Festbettadsorption an granulierte Aktivkohle und (3) Ozonung zur Spurenstoffentfernung, um zukünftige Anforderungen an Oberflächengewässer zu erfüllen. Die mittels Pilotversuchen gewonnenen Ergebnisse verdeutlichen, dass sowohl Ozonung als auch Aktivkohle sinnvoll mit der Flockungsfiltration kombiniert werden können. Alle untersuchten Verfahrensvarianten sind geeignet, den Spurenstoffeintrag kommunaler Kläranlagen signifikant zu verringern und gleichzeitig die Zielwerte für die suspendierten Stoffe (TSS < 1 mg/L) und Gesamtphosphor (TP < 0,1 mg/L) sicher einzuhalten. Es erfolgt eine zusätzliche Entfernung von CSB und DOC. Die Entfernung der einzelnen Spurenstoffe ist stoffspezifisch. Sie ist außerdem abhängig von der Konzentration des im Wasser vorliegenden gelösten organischen Kohlenstoffs (DOC) und der Dosis von Aktivkohle bzw. Ozon, aber unabhängig von der Ausgangskonzentration der Spurenstoffe. Für ausgewählte Indikatorsubstanzen wurden Dosis-Wirkungsbeziehungen für die Adsorption an Aktivkohle und die Reaktion mit Ozon ermittelt und an den Pilotanlagen überprüft. Der spezifische Absorptionskoeffizient bei 254 nm (SAK254) ist eine geeignete Größe zur Steuerung und Überwachung der Spurenstoffentfernung und sowohl für die Ozonung als auch die Adsorption an Aktivkohle aussagekräftig. Eine Regelung der Ozonung mittels SAK254 wurde im Pilotmaßstab getestet. Die Pilotuntersuchungen wurden darüber hinaus durch ein toxikologisches Monitoring begleitet, bei dem unterschiedliche, etablierte Untersuchungsmethoden eingesetzt, aber keine Hinweise auf humantoxikologische bzw. ökotoxikologische Risiken aufgezeigt wurden, auch nicht durch Oxidationsprodukte der Ozonung. Um eine vollständige ökotoxikologische Bewertung zu ermöglichen, müssen die Methoden weiter entwickelt werden. Neben den verfahrenstechnischen Untersuchungen wurden für die Verfahrensvarianten auch eine Kostenschätzung und Ökobilanz erstellt. Sowohl die Gesamtkosten als auch die Umweltwirkungen einer weitergehenden Phosphorentfernung mit Flockungsfiltern erhöhen sich deutlich, wenn mittels Ozon oder Aktivkohle zusätzlich auch Spurenstoffe entfernt werden sollen.

In recent years several ways of recovering phosphorous from municipal wastewater have been developed. Depending on the applied technology the recovered products as well as the quality of sewage sludge vary significantly concerning the concentrations of heavy metals and organic residues. Within WA 4 “environmental, economic and risk assessment of P recovery options” of the P-REX project a quantitative risk assessment of substances in phosphorus products for humans and environment is intended. In this deliverable risk assessment is done as a relative risk ranking for PCDD/F, dl-PCB, PAH, As, Cd, Cr, Cu, Hg, Ni, Pb and Zn between seven secondary phosphate fertilizers from wastewater stream, sewage sludge, mono-incinerated ash from sewage treatment and conventional phosphorus fertilizers.

Managed aquifer recharge (MAR) is a widely accepted method for augmenting water supplies for potable and non-potable use. The success of the MAR system is often defined by a substantial removal of chemical and biological contaminants during subsurface passage. To determine removal rates and to differentiate between removal and overall attenuation due to dilution, estimation of mixing proportions is a key element of tracer applications. This report provides an overview of tracers suitable for MAR and discusses advantages and disadvantages for each tracer. The ideal tracer may be defined by: a natural or anthropogenic origin, a clear uneven distribution in the studied system (e.g. sharp contrast between source and native groundwater), non-toxicity (human and environmental), easy and cost-effective measurement, and a conservative (neither sorbed nor (bio-)chemical reactive) or at least predictable chemical or physical behavior. A huge number of tracers exist, each with advantages and disadvantage. Tracers can be dissolved (e.g. chloride, bromide), stable or radioactive isotopes (e.g. 18O, 3H), gaseous (e.g. SF6) or a physical properties (e.g. temperature). The use of heat as a tracer has several advantages over hydrochemical tracers. Temperature is inexpensive, easy and a robust parameter to measure. In contrast to chemical tracers, no laboratory analysis is required and the data is available immediately. Finally, a multi tracer approach (= 2 tracers) is always recommended, because the ideal tracer is rarely found. A reasonable combination is at least one conservative tracer (e.g. stable isotopes of water) with a retarded tracer (e.g. temperature) to evaluate short travel times from the point of recharge (e.g. riverbed or pond) to the recovery well.

This report provides the reader with an overview of assessment methodologies used within DEMOWARE and the specific features when using QMRA, QCRA, LCA, and WFP approach for the assessment of water reuse systems. For the actual application of LCA and water footprint databases and assessment software is needed. Therefore, three complementing goals shall be achieved: (i) to provide practitioners with the principles, methods and limitations of QMRA, QCRA, LCA and WFP (ii) to provide LCA, WFP, RA practitioners with additional information when using the respective method for the assessment of water reuse systems. For QMRA a summary of guidelines and default values is collected from different guidelines documents (WHO, Australia, US-EPA), which allow a first simplified and thus user friendly risk estimate.