Optimisation of organic compound removal in artificial recharge systems by redox control and enhanced oxidation. Final Report of OXIRED - Phase 2

Optimisation of organic compound removal in artificial recharge systems by redox control and enhanced oxidation. Final Report of OXIRED - Phase 2

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.