Advanced oxidation processes for waste water treatment: from laboratory-scale model water to on-site real waste water.

A process combining three steps has been developed as a tertiary treatment for waste water in order to remove micropollutants not eliminated by a conventional waste water treatment plant (WWTP). These three processes are ozonation, photocatalysis and granulated activated carbon adsorption. This process has been developed through three scales: laboratory, pilot and pre-industrial scale. At each scale, its efficiency has been assessed on different waste waters: laboratory-made water, industrial waste water (one from a company cleaning textiles and another from a company preparing culture media, both being in continuous production mode) and municipal waste water. At laboratory scale, a TiO2-based photocatalytic coating has been produced and the combination of ozonation-UVC photocatalytic treatment has been evaluated on the laboratory-made water containing 22 micropollutants. The results showed an efficient activity leading to complete or partial degradation of all compounds and an effective carbon for residual micropollutant adsorption was highlighted. Experiments at pilot scale (100 L of water treated at 500 L/h from a tank of 200 L) corroborated the results obtained at laboratory scale. Moreover, tests on municipal waste water showed a decrease in toxicity, measured on Daphnia Magma, and a decrease in micropollutant concentration after treatment. Finally, a pre-industrial container was built and evaluated as a tertiary treatment at the WWTP Duisburg-Vierlinden. It is shown that the main parameters for the efficiency of the process are the flow rate and the light intensity. The photocatalyst plays a role by degrading the more resistant micropollutants. Adsorption permits an overall elimination >95% of all molecules detected.

Advanced photocatalytic oxidation processes for micropollutant elimination from municipal and industrial water.

The objective of this study was to develop and validate an innovative technology to ensure efficient elimination of different types of micropollutants and toxic compounds in waste water. The process is a tertiary treatment process, which can be easily integrated into municipal and industrial waste water treatment plants. It is based on oxidation by ozone and subsequent photocatalytic treatment. After development and validation of this system at laboratory scale, the solution was tested at pilot scale. The first part of this work was to develop a TiO2-based film on glass substrate, characterize its physico-chemical properties and optimize its composition at laboratory scale to be photoactive on the degradation of model water containing several pollutants. The model water consisted of a mixture of 22 major micropollutants including pesticides, plasticizers, brominated compounds, and pharmaceuticals. The best photocatalyst for the degradation of the selected micropollutants was a TiO2 coating doped with 2 wt% of Ag and where 10 wt% P25 was added. Then, in order to scale up the process, its deposition on steel substrates was tested with dip and spray coating at laboratory scale. Calcination parameters were optimized to limit steel corrosion while keeping similar photoactive properties regarding the degradation of the model polluted water. The optimized solution was deposited by spray coating in a pilot scale reactor in order to assess its efficiency in a pilot water treatment plant.

Cost-effective reduction of micro pollutants in the water cycle - Case study on iodinated contrast media.

Surface waters, especially in densely populated areas, are facing multiple anthropogenic pressures. Micro pollutants are of growing concern. Improved analytical methods are used to focus on substances like ICM with a (high) potential of hazardous effects against water organisms or the water quality in general ICM are essential for instance in computer tomographic examinations in medical facilities. Discharge of ICM to the sewer system occurs via human urine excretions. Common waste water treatment plants do not eliminate these substances completely. Therefore, increasing concentrations are found in the rivers worldwide. The project MERK'MAL explored a potentially cost-effective measure to reduce ICM in the River Ruhr, located in Germany, North Rhine-Westphalia. The results from this pilot study show that urine bags are an effective measure to reduce ICM concentrations. During the urine collection with bags measurements of ICM concentrations have shown a reduction, compared to the baseline concentration that was measured at the same sampling point in the effluent of the corresponding waste water treatment plant. The ICM reduction ranged between 20 and 34% for the mean values and between 7 and 33% for the median value. Additional payment equivalent costs per examination with ICM are approx. 3.36 €, full costs including imputed costs are expected in a cost range of 5.38 € to 6.09 € per examination. The extension of the study is envisioned, helping to sustainably enhance water quality in the River Ruhr in terms of ICM concentrations.

Occurence and Prioritization of Pharmaceutical Active Compounds in Domestic/Municipal Wastewater Treatment Plants.

In this study, pharmaceutically active compounds (PhACs) were analyzed in the influent and effluent of a domestic wastewater treatment plant in Turkey and a municipal wastewater treatment plant in Germany and the toxicity of these wastewaters were estimated using a toxic unit (TU) approach. A total of 21 and 32 PhACs were detected in the domestic wastewater and the municipal wastewater, respectively. The TUs estimated for PhACs in municipal wastewater were higher than the TUs estimated for PhACs present in domestic wastewater. The levels of the anti-anxiety drug, oxazepam were estimated to be in the high risk category (HQ > 10) in both wastewaters. In bench-scale tests with ozonation, the removals of four PhACs in the municipal wastewater were investigated. At a dose of 2 mg/L ozone, 97%-98% of diclofenac and carbamazepine were removed. The lowest removal rate at 71% was observed for metoprolol.

Investigation of full-scale ozonation at a municipal wastewater treatment plant using a toxicity-based evaluation concept.

Effluents from municipal wastewater treatment plants (WWTPs) are known to be point sources of micropollutants for surface waters. The aim of this study was to examine a reconstructed full-scale ozonation equipped with a pump-injector system for ozone (O3) dosage and a fluidized moving-bed reactor as biological posttreatment at a municipal WWTP utilizing an effect-directed approach. This approach consists of chemical analysis in combination with toxicological tests for the assessment of treatment efficiency of the plant. Chemical analysis showed elimination rates > 80% for pharmaceuticals and industrial chemicals. Analysis of endocrine disruptors was limited due to substance concentrations below the limit of detection (LOD). Estrogenic activity was detected by the Arxula Adeninivorans yeast estrogen screen (A-YES) at low concentrations (pg to ng EEQ/l range). Estrogenic activity was reduced by more than 90% after ozonation. In contrast, androgenic activity (measured in the Adeninivorans yeast androgen screen, A-YAS) was still found after O3 treatment and after biological posttreatment, which is consistent with the data obtained by chemical analysis. Furthermore, no marked genotoxic or cytotoxic effects were observed after ozonation using the alkaline comet and 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromid (MTT) assays, respectively. Results suggest that the applied specific O3 dose of 0.4 mgO3/mgDOC is a safe operation setup in terms of toxicologically relevant transformation products. In addition, no adverse effects on primary producers, as evidenced by algae growth inhibition tests, were detected. The monitored biofilm growth in the biological posttreatment exhibited a steady state after one month. Based on computational fluid dynamics (CFD) simulations and biomass, one might conclude that O3 did not apparently enter biological posttreatment to a great extent and that hydraulic retention time in the O3 reactor was sufficient. Our data demonstrate the effectiveness of a full-scale O3 treatment in combination with a fluidized moving-bed reactor as biological posttreatment for the reduction of a majority of micropollutants without the release of relevant toxic transformation products as assessed by a chemical and toxicity-based approach.

Characterization and toxicity of hospital wastewaters in Turkey.

The aim of the study was to present first preliminary characterization of Turkish hospital wastewaters, their environmental risk, and a method for toxicity assessment. The hospital wastewater samples were collected from two of the largest medical faculty hospitals and a training and research hospital in Istanbul, Turkey. The samples from the selected hospitals were taken as grab samples on March 2014. Overall, 55 substances including pharmaceuticals and their metabolites, pesticides, and corrosion inhibitors were analyzed in all hospital wastewaters. Analysis of toxicity and the antibiotic resistance bacteria were investigated in addition to the chemical analysis in the wastewater of one hospital. Hazard quotients (HQs) and toxic units (TUs) were calculated as basis of the environmental risk assessment. Fourteen pharmaceuticals in hospital wastewater (HWW) were classified as "high risk" with HQ > 10. HQHWW values higher than 100 were determined for five antibiotics and one analgesic, namely, ofloxacin, clarithromycin, ciprofloxacin, sulfapyridine, trimethoprim, and diclofenac. Ofloxacin with an HQHWW of 9090 was observed to be the most hazardous compound. HQ and TU values of the wastewater treatment plant (WWTP) effluent dropped significantly due to dilution in the sewer. Further elimination by biological degradation or adsorption was observed only in some cases. However, the decreased HQWWTPeffluent values do not the change environmental load significantly. Therefore, advanced treatment processes should be applied to remove the persistent compounds. In combination with the results on antibiotic resistance, we would prefer on-site treatment of hospital wastewater. Toxicological assessment was performed using cytotoxic and mutagenic screening tests. The results of the Ames assay showed that the native hospital wastewaters had strongly mutagenic activity with a ≤10-fold increase relative to negative controls. The mutagenic potentials of the samples were generally concentration and metabolic activation dependent. Multiple antibiotic resistances were demonstrated with the tested isolates to ciprofloxacin, trimethoprim, and ceftazidime. This study demonstrates that the hospital wastewaters in Istanbul exhibit strong environmental and toxicological risks, as well as high multiple drug resistance to commonly used antibiotics.

Toxicity of the micropollutants Bisphenol A, Ciprofloxacin, Metoprolol and Sulfamethoxazole in water samples before and after the oxidative treatment.

The amount of organic micropollutants detected in surface waters increases steadily. Common waste water treatment plants are not built to remove these substances. Thus there is a need for new technologies. A promising technology is the use of advanced oxidation processes through which organic micropollutants can be removed from waste water. However, the formation of oxidation by-products is likely and needs to be investigated since the by-products not only differ from their parent compounds in regard to their chemical and physical properties but they can also differ in toxicity. Therefore this study was designed to combine chemical and toxicological analyses of the advanced oxidation (O3 [5mg/L] or UV/H2O2 [Hg-LP lamp; 15W; 1g/L H2O2]) of waste water treatment plant effluents and pure water. Effluent samples from conventional activated sludge waste water treatment (mechanical treatment, activated sludge basin, and primary as well as secondary treatment steps) and high-purity deionized water (pure water) were spiked with Bisphenol A, Ciprofloxacin, Metoprolol or Sulfamethoxazole and treated with O3 or UV/H2O2. For the toxicological analyses mammalian cells (CHO-9, T47D) were exposed to the water samples for 24h and were tested for cytotoxicity (MTT Test), genotoxicity (Alkaline Comet Assay) and estrogenicity (ER Calux(®)). The results indicate that the oxidative treatment (O3 or UV/H2O2) of Bisphenol A, Metoprolol, Sulfamethoxazole or Ciprofloxacin in waste water did not result in toxic oxidation by-products, whereas the UV/H2O2 treatment of Bisphenol A and Ciprofloxacin in pure water resulted in by-products with cytotoxic but no estrogenic effects after 60min.

Temperature and pH-stability of commercial stationary phases.

In this paper, the temperature and pH stability of silica-based RP stationary phases were investigated. Furthermore, nonsiliceous phases like a polymeric column based on polystyrene divinylbenzene and a polybutadiene coated zirconium dioxide column were also included. The columns were heated up to 150 degrees C at dynamic conditions, which means that the eluent consisting of water and methanol (90:10, v/v) was continuously purged through the packed bed. After every 5 h, the columns were cooled down to room temperature and the efficiency was measured by injecting a test sample based on the Neue test. It could be shown that some stationary phases exhibited a very good temperature stability at the test conditions specified above.