Zusammenfassung

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.

Zusammenfassung

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.

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