In 2015, the town of El Port de la Selva in Spain implemented soil-aquifer treatment (SAT) using tertiary treated wastewater effluents to replenish the local potable aquifer. This study evaluated the initial phase of this indirect potable water reuse system including a characterization of hydraulic conditions in the aquifer and monitoring of microbial contaminants and 151 chemicals of emerging concern (CECs). The combined treatment resulted in very low abundances of indicator bacteria, enteric viruses and phages in the monitoring wells after three days of infiltration and a reduction of antibiotic microbial resistance to background levels of local groundwater. After tertiary treatment, 94 CECs were detected in the infiltration basin of which 15 chemicals exceeded drinking water thresholds or health-based monitoring trigger levels. Although SAT provided an effective barrier for many chemicals, 5 CECs were detected above health-based threshold levels in monitoring wells after short hydraulic retention times. However, additional attenuation is expected due to dilution prior to abstraction via downstream drinking water wells and during granular activated carbon (GAC) filtration, which was recently installed to mitigate residual CECs. Overall, the results demonstrate that indirect potable water reuse can be a reliable option for smaller communities, if related risks from microbial and chemical contaminants are adequately addressed by tertiary treatment and subsequent SAT, providing sufficient hydraulic retention times for pathogen decay and CEC removal.

Subsurface passage as utilized during bank filtration and artificial groundwater recharge has shown to be an effective barrier for multiple substances present in surface waters during drinking water production. Additionally it is widely used as polishing step after wastewater treatment. However, there are limitations concerning the removal of DOC and specific trace organics. The project ”OXIRED“ aims at assessing possibilities to overcome these limitations by combining subsurface passage with oxidation by ozone. Results from the first phase of the project have demonstrated that oxidation with ozone is a suitable method to reduce the concentrations of several relevant trace organic compounds (e.g. carbamazepine, sulfamethoxazole) and to significantly enhance biodegradation of DOC during subsequent soil passage. For efficient removal of DOC in the soil columns, specific ozone consumptions of 0.6 to 0.7 mgO3/DOC0 were sufficient. Project objectives in OXIRED-2 were to i) verify results from laboratory scale experiments at a larger scale with longer retention times, ii) study feasibility under field conditions with seasonal variations by operating a pilot unit, iii) evaluate the formation of oxidation by-products and their persistence during subsurface passage and iv) propose a standardized test protocol to analyse benefits of ozonation and artificial groundwater recharge at different sites. To investigate effects of ozonation on groundwater recharge with longer retention times, a technical scale column system with a length of 30 m and a hydraulic retention time of approximately six weeks was operated at the UBA’s experimental site in Berlin Marienfelde. Pilot studies were conducted at Lake Tegel using an ozone unit from ITT-Wedeco with a 4 g/h generator and subsequent slow sand filtration. Reduction of bromate was assessed in laboratory scale soil columns under different redox conditions. In addition, anoxic reduction of bromate was evaluated in a diploma thesis at TU Berlin. To analyse effects of DOC removal after ozonation, a standardized test protocol using recirculating columns was proposed and tested. Results from the different experiments confirmed the conclusions of the first phase of the project. Removal of surface water DOC during infiltration significantly increased with preozonation. In pilot studies, effluent DOC of approximately 4.7 mg/L after 1 d of retention time was measured, which is comparable to residual DOC from artificial groundwater recharge in Berlin Tegel after 30 days retention time [1]. In addition, strong effects of temperature on DOC removal were observed. During experiments with ozonation, overall DOC reduction decreased from approximately 40% in October to about 30% in the end of November. Biological testing of slow sand filter effluent revealed no genotoxic or cytotoxic effects in the water prior to further infiltration into the aquifer. Many persistent trace compounds were efficiently transformed during ozonation with specific ozone doses of 0.8 mg O3/mg DOC0. For example, realistic surface water concentrations of carbamazepine, sulfamethoxazole, phenazone and bentazone were reduced below the limits of quantification (LOQ). Primidone was only partly transformed during ozonation (70%). Since primidone is persistent during infiltration, a breakthrough in combined ozonation and artificial recharge can be expected. Also the substances MTBE and ETBE, the pesticide atrazine and some metabolites detected in Lake Tegel persist partially during treatment with ozone and subsequent groundwater recharge. For efficient transformation of these substances, higher ozone doses or an optimisation of the oxidation process, for example as advanced oxidation process (AOP), should be considered. Efficient reduction of the concentration of adsorbable organic iodine (AOI), an indicator for x-ray contrast media, during ozonation or infiltration was not observed. In contrast, adsorbable organic bromine decreased by 70 - 80 % during ozonation. Formation of the oxidation by-product bromate during ozonation of Lake Tegel water with a specific ozone consumption of up to 1.0 mg O3/mg DOC0 was below the limit of the German drinking water directive. Removal during subsurface passage was observed under anoxic conditions in presence of biodegradable organic carbon. Since artificial recharge after ozonation is likely aerobic, no significant reduction of bromate can be expected. Thus, formation of bromate needs to be controlled during surface water ozonation. Formation of nitrosamines was monitored in batch experiments with a specific ozone consumption of up to 1.15 mg O3/mg DOC0. No formation of nitrosamines including NDMA (LOQ: 5 ng/L) was observed. Operating a preceding bank filtration step will reduce ozone demand for efficient DOC removal. In addition, problems with particles from source water can be minimised. However, additional energy consumption for operation of extraction wells has to be taken into account. Overall, the presented results confirm that the objectives of enhanced removal of trace organics and DOC by combining ozonation and subsurface passage are well met. Further investigations need to focus on seasonal variations in long-term pilot studies and the formation, retention and toxicity of transformation products.

Subsurface passage as utilized during river bank filtration and artificial groundwater recharge has shown to be an effective barrier for multiple substances present in surface waters during drinking water production. Additionally it is widely used as polishing step after wastewater treatment. However, there are limitations concerning the removal of DOC and specific trace organics. The project ”OXIRED“ aims at assessing possibilities to overcome these limitations by combining subsurface passage with pre-oxidation by ozone. In the first phase of the project, laboratory-scale column experiments were conducted in order to quantify removal for different settings under varying conditions. In a previous study different combinations of advanced oxidation and subsurface passage were evaluated concerning their potential removal efficiency and practical implementation on the basis of existing, published experiences and theoretical considerations. Two different scenarios were identified as promising for experiments in laboratory-scale columns with surface water and sewage treatment plant effluent: (A) surface water - oxidation - groundwater recharge and (B) surface water - short bankfiltration - oxidation - groundwater recharge. The investigations were designed to lead to recommendations for the implementation of a combined system of subsurface passage and advanced oxidation in pilot scale experiments that will be carried out in the second phase of the project. Prior to column experiments, batch tests following the RCT-concept by Elovitz and von Gunten (1999) were carried out to characterize the reaction of ozone with the investigated water qualities [1]. Additional batch ozonation tests with subsequent analysis of biodegradable dissolved organic carbon (BDOC) were conducted in order to determine optimal ozone doses for DOC removal in column experiments. For laboratory-scale experiments a set of 8 soil columns (length: 1 m; diameter: 0.3 m) was operated at TUB to evaluate the effects of pre-ozonation of different source waters (secondary effluent, surface water, bank filtrate). Ozonation was conducted with gaseous ozone in a 13-L stirred tank reactor. Specific ozone doses of 0.7 mg O3/mg DOC0 and 0.9 mg O3/mg DOC0 were investigated. Trace organic compounds to be targeted were identified in a prior literature study on existing data on subsurface removal. Results from laboratory-scale soil column experiments led to recommend specific ozone doses (z) of 0.7 mg O3/mg DOC0 for the following technical- and pilot-scale applications. Removal of surface water DOC in the soil columns was increased from 22% without ozonation to 40% (z = 0.7) and 45% (z = 0.9) with preozonation and the DOC in the column effluent reached the level of tap water in Berlin within less than one week of retention time. At bank filtration and artificial recharge sites in Berlin similar removal rates were only observed within 3 - 6 months of retention [2]. The transformation of many trace compounds was efficient with specific ozone doses of 0.6-0.7 mg O3/mg DOC0. Realistic surface water concentrations of carbamazepine,sulfamethoxazole, diclofenac and bentazone were reduced below the limits of quantification (LOQ). The pesticides diuron and linuron were reduced close to LOQ. The substances MTBE, ETBE and atrazine were only partly transformed during ozonation. For efficient transformation of these substances, higher ozone doses or an optimisation of the oxidation process, for example as advanced oxidation process (AOP), should be considered. Operating a preceding bank filtration (scenario B) will enhance the transformation efficiency of MTBE and ETBE. With similar ozone consumption the transformation of MTBE and ETBE was increased by 27-31% and 28-33% of the original removal, respectively. Other investigated compounds were efficiently transformed during ozonation of surface water independently of the preceding bank filtration step. For the removal of bulk organic carbon only little improvement was observed for scenario B. Overall DOC removal increased from 45% with direct ozonation of surface water to up to 50% with a preceding soil column. Despite the presence of relevant bromide concentrations (~ 100 µg/L) formation of the oxidation by-product bromate was not observed (< 5 µg/L). However, this could also be a result of analytical problems, as later spiking tests showed. Formation of brominated organic compounds was also not observed. Adsorbable organic bromide (AOBr) even decreased by 50 - 60% for secondary effluent and 80 - 90% for surface water. The reduction of AOBr concentrations was accompanied by an increase of inorganic bromide by up to 40 µg/L during ozonation of surface water. In the two conducted in vitro genotoxicity tests (Ames test, micronucleus assay) no genotoxicity caused by ozonation of water samples was observed. Testing for cytotoxicity (glucose consumption rate, ROS generation) showed positive results in several samples. However, a systematic attribution of toxic effects to ozonation or subsequent soil passage was not possible. Reasons for cytotoxic effects were not evaluated within the scope of this project but it is assumed that they were caused by unknown cofactors. These results show that the objectives of enhanced removal of trace organics and DOC by combining ozonation and subsurface passage are well met. Further investigations need to confirm this for the pilot scale, especially taking into account the formation, retention and toxicity of oxidation by-products.

Investigations on the behavior of bulk organics and trace organic compounds in a temperated soil column system are reported. Objective of the research was to assess the importance of temperature for the degradation of bulk and trace organics. The analysis of the bulk organic behavior showed a fast mineralization of easy degradable organic carbon in the first few centimeters of the columns, which does not seem to be temperature-dependent. Along the further infiltration path an influence of the different temperatures on the bioactivity was clearly visible. However, a significant increase of mineralization potential of bulk organic compounds with increasing temperature was shown. The monitoring of the single organic pollutants Iopromide, Sulfamethoxazole and naphthalenedisulfonic acids showed that temperature has an influence on the degradation behavior of the monitored compounds. In most cases higher temperatures increased the mineralization potential.

Die TU-Forschungsgruppe beschäftigt sich mit dem Verhalten von DOC und organischen Einzelstoffen bei der Uferfiltration. Die Forschung soll Einblick in die Vielzahl von Einflussfaktoren geben, die das Verhalten der Organik in der Bodenpassage beeinflussen. Unterschiedliche Redoxverhältnisse, Aufenthaltszeiten und Bodenbeschaffenheiten beeinflussen den Abbau der Organik. Die Forschung im Rahmen des NASRIProjektes konzentrierte sich in der ersten Phase auf ein umfangreiches Feldmonitoring, welches im Zeitraum Mai 2002August 2005 durchgeführt wurde. Dazu wurden drei Feldstandorte in Berlin ausgewählt, an welchen ein deutlicher Einfluss von behandeltem Abwasser auf das Oberflächenwasser vorliegt. Zusätzlich wurde eine Vielzahl von Experimenten an Bodensäulenanlagen durchgeführt. Neben einem 30 mBodensäulensystem in Berlin- Marienfelde, wurden eine redoxgeregelte Bodensäulenanlage und eine temperaturgeregelte Bodensäulenanlage für die Untersuchungen aufgebaut. Die Feldund Bodensäulenproben wurden mittels DOC, SAK, LC-OCD, differenziertem AOX und Spurenstoffanalytik (HPLC-FLD und HPLC-MS/MS) untersucht. Die Ergebnisse zeigten, dass sowohl oxische als auch anoxisch/anaerobe Infiltrationsbedingungen zu einem ähnlich niedrigen DOC führen können. Unter oxischen Verhältnissen ist zur Mineralisierung des BDOC nur eine einmonatige Bodenpassage notwendig, während es unter anoxisch/anaeroben Verhältnissen aufgrund der langsameren Abbaukinetik bis zu 6 Monate dauern kann. Die Ergebnisse der DOCFraktionierung mittels LC-OCD zeigten, dass die Fraktion der Polysaccharide unter allen Bedingungen sehr schnell abgebaut wurde. Dagegen wurde für die anderen Fraktionen (Huminstoffe, Building Blocks etc.) nur eine partielle Entfernung beobachtet. Bezüglich der Spurenstoffe konnte gezeigt werden, dass das Röntgenkontrastmittel Iopromid in allen Felduntersuchungen schnell entfernt wurde. In den Bodensäulenexperimenten zeigte sich, dass die Entfernung durch Metabolisierung und nicht durch Mineralisierung zustande kam. Das Antibiotikum Sulfamethoxazole wurde unter anoxisch/anaeroben Verhältnissen effektiver entfernt (bis zu 80%), während unter oxischen Bedingungen maximal 50% der Ausgangskonzentration abgebaut wurden.

The present report characterizes the field sites Lake Tegel and Lake Wannsee as well as the artificial recharge site GWA Tegel in terms of their clogging layer, sedimentary, hydraulic and hydrochemical properties. As a result, a solid basis for the interpretation of specific compounds evaluated within NASRI and for subsequent modeling and quantification of the data is given. Major problems or difficulties where identified, in order to focus investigations on aspects not fully understood to date in the next project phase. The combination of different tracers enables the interpretation of the flow regime. With the help of T/He analysis, ages of different water bodies can be estimated. The analysis of tracer showing distinct seasonal variations is used to estimate travel times while water constituents which are either mainly present in the bank filtrate or the background water are used for mixing calculations. The proportions of treated wastewater in the surface water were estimated in front of the transects. The surface water composition varies largely both in time and space, which is a problem at Wannsee, where the surface water sampling point is not representative for the bank filtration input. Estimates for travel times of the bank filtrate to individual observation and production wells are given and vary between days and several months. The production wells are a mixture of bank filtrate and water from inland of the wells and deeper aquifers, proportions of bank filtrate are given where possible to differentiate between contaminant removal and dilution. They vary between < 20 and > 80 %. The new observation wells enable a vertical differentiation of the infiltrate. It becomes clear that at Tegel and Wannsee, there is a strong vertical succession towards larger proportions of considerably older bank filtrate with depth. At the Wannsee transect, the observation wells deeper than the lake do not reflect the surface water signal at all. It will be important to combine the new information with hydraulic information of existing flow models (mainly of the IGB “model” group). The evaluation of the redox conditions shows that redox successions proceed with depth rather than (only) in flow direction. In addition, the redox zoning (as characterised by the appearance or disappearance of redox sensitive species) is very transient. The zones are much wider in winter than in summer, in particular at the artificial recharge site GWA Tegel, probably due to temperature effects. This poses a challenge for the desired modelling and the interpretation of data from redoxsensitive substances.