Martin Petkovšek

Removal of pharmaceuticals from wastewater by biological processes, hydrodynamic cavitation and UV treatment

To augment the removal of pharmaceuticals different conventional and alternative wastewater treatment processes and their combinations were investigated. We tested the efficiency of (1) two distinct laboratory scale biological processes: suspended activated sludge and attached-growth biomass, (2) a combined hydrodynamic cavitation-hydrogen peroxide process and (3) UV treatment. Five pharmaceuticals were chosen including ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac, and an active metabolite of the lipid regulating agent clofibric acid. Biological treatment efficiency was evaluated using lab-scale suspended activated sludge and moving bed biofilm flow-through reactors, which were operated under identical conditions in respect to hydraulic retention time, working volume, concentration of added pharmaceuticals and synthetic wastewater composition. The suspended activated sludge process showed poor and inconsistent removal of clofibric acid, carbamazepine and diclofenac, while ibuprofen, naproxen and ketoprofen yielded over 74% removal. Moving bed biofilm reactors were filled with two different types of carriers i.e. Kaldnes K1 and Mutag BioChip™ and resulted in higher removal efficiencies for ibuprofen and diclofenac. Augmentation and consistency in the removal of diclofenac were observed in reactors using Mutag BioChip™ carriers (85%±10%) compared to reactors using Kaldnes carriers and suspended activated sludge (74%±22% and 48%±19%, respectively). To enhance the removal of pharmaceuticals hydrodynamic cavitation with hydrogen peroxide process was evaluated and optimal conditions for removal were established regarding the duration of cavitation, amount of added hydrogen peroxide and initial pressure, all of which influence the efficiency of the process. Optimal parameters resulted in removal efficiencies between 3-70%. Coupling the attached-growth biomass biological treatment, hydrodynamic cavitation/hydrogen peroxide process and UV treatment resulted in removal efficiencies of >90% for clofibric acid and >98% for carbamazepine and diclofenac, while the remaining compounds were reduced to levels below the LOD. For ibuprofen, naproxen, ketoprofen and diclofenac the highest contribution to overall removal was attributed to biological treatment, for clofibric acid UV treatment was the most efficient, while for carbamazepine hydrodynamic cavitation/hydrogen peroxide process and UV treatment were equally efficient.

Use of hydrodynamic cavitation in (waste)water treatment.

The use of acoustic cavitation for water and wastewater treatment (cleaning) is a well known procedure. Yet, the use of hydrodynamic cavitation as a sole technique or in combination with other techniques such as ultrasound has only recently been suggested and employed. In the first part of this paper a general overview of techniques that employ hydrodynamic cavitation for cleaning of water and wastewater is presented. In the second part of the paper the focus is on our own most recent work using hydrodynamic cavitation for removal of pharmaceuticals (clofibric acid, ibuprofen, ketoprofen, naproxen, diclofenac, carbamazepine), toxic cyanobacteria (Microcystis aeruginosa), green microalgae (Chlorella vulgaris), bacteria (Legionella pneumophila) and viruses (Rotavirus) from water and wastewater. As will be shown, hydrodynamic cavitation, like acoustic, can manifest itself in many different forms each having its own distinctive properties and mechanisms. This was until now neglected, which eventually led to poor performance of the technique. We will show that a different type of hydrodynamic cavitation (different removal mechanism) is required for successful removal of different pollutants. The path to use hydrodynamic cavitation as a routine water cleaning method is still long, but recent results have already shown great potential for optimisation, which could lead to a low energy tool for water and wastewater cleaning.

Observations of cavitation erosion pit formation

Previous investigations showed that a single cavitation bubble collapse can cause more than one erosion pit (Philipp & Lauterborn [1]). But our preliminary study showed just the opposite - that in some cases a single cavitation pit can result from more than one cavitation event. The present study shows deeper investigation of this phenomenon. An investigation of the erosion effects of ultrasonic cavitation on a thin aluminum foil was made. In the study we observed the formation of individual pits by means of high speed cameras (>1000 fps) and quantitatively evaluated the series of images by stereoscopy and the shape from shading method. This enabled the reconstruction of the time evolution of the pit shape. Results show how the foil is deformed several times before a hole is finally punctured. It was determined that larger single pits result from several impacts of shock waves on the same area, which means that they are merely special cases of pit clusters (pit clusters where pits overlap perfectly). Finally it was shown that a thin foil, which is subjected to cavitation, behaves as a membrane. It was concluded that the physics behind erosion depends significantly on the means of generating cavitation (acoustic, hydrodynamic, laser light) and the specimen characteristics (thin foil, massive specimen), which makes comparison of results of materials resistance to cavitation from different experimental set-ups questionable. Further development of the shape from shading method in the scope of cavitation erosion testing will enable better evaluation of cavitation erosion models.

A novel rotation generator of hydrodynamic cavitation for waste-activated sludge disintegration

The disintegration of raw sludge is very important for enhancement of the biogas production in anaerobic digestion process as it provides easily degradable substrate for microorganisms to perform maximum sludge treatment efficiency and stable digestion of sludge at lower costs. In the present study the disintegration was studied by using a novel rotation generator of hydrodynamic cavitation (RGHC). At the first stage the analysis of hydrodynamics of the RGHC were made with tap water, where the cavitation extent and aggressiveness was evaluated. At the second stage RGHC was used as a tool for pretreatment of a waste-activated sludge (WAS), collected from wastewater treatment plant (WWTP). In case of WAS the disintegration rate was measured, where the soluble chemical oxygen demand (SCOD) and soluble Kjeldahl nitrogen were monitored and microbiological pictures were taken. The SCOD increased from initial 45 mg/L up to 602 mg/L and 12.7% more biogas has been produced by 20 passes through RGHC. The results were obtained on a pilot bioreactor plant, volume of 400 L.

Shear-induced hydrodynamic cavitation as a tool for pharmaceutical micropollutants removal from urban wastewater

In this study, the removal of clofibric acid, ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac residues from wastewater, using a novel shear-induced cavitation generator has been systematically studied. The effects of temperature, cavitation time and H2O2 dose on removal efficiency were investigated. Optimisation (50°C; 15 min; 340 mg L(-1) of added H2O2) resulted in removal efficiencies of 47-86% in spiked deionised water samples. Treatment of actual wastewater effluents revealed that although matrix composition reduces removal efficiency, this effect can be compensated for by increasing H2O2 dose (3.4 g L(-1)) and prolonging cavitation time (30 min). Hydrodynamic cavitation has also been investigated as either a pre- or a post-treatment step to biological treatment. The results revealed a higher overall removal efficiency of recalcitrant diclofenac and carbamazepine, when hydrodynamic cavitation was used prior to as compared to post biological treatment i.e., 54% and 67% as compared to 39% and 56%, respectively. This is an important finding since diclofenac is considered as a priority substance to be included in the EU Water Framework Directive.

The issue of cavitation number value in studies of water treatment by hydrodynamic cavitation

Within the last years there has been a substantial increase in reports of utilization of hydrodynamic cavitation in various applications. It has came to our attention that many times the results are poorly repeatable with the main reason being that the researchers put significant emphasis on the value of the cavitation number when describing the conditions at which their device operates. In the present paper we firstly point to the fact that the cavitation number cannot be used as a single parameter that gives the cavitation condition and that large inconsistencies in the reports exist. Then we show experiments where the influences of the geometry, the flow velocity, the medium temperature and quality on the size, dynamics and aggressiveness of cavitation were assessed. Finally we show that there are significant inconsistencies in the definition of the cavitation number itself. In conclusions we propose a number of parameters, which should accompany any report on the utilization of hydrodynamic cavitation, to make it repeatable and to enable faster progress of science and technology development.

Combined Numerical and Experimental Investigation of the Cavitation Erosion Process

We are comparing results of numerical simulations a gainst high speed simultaneous observations of cavitation and cavitation erosion. We performed fully compressible, cavitating flow simulations to resolve the formation of the sh ock waves at cloud collapse – these are believed to be directly related to the formation of the damage. Good agreements were noticed between calculations and tests. Two high pressure p eaks were found during one cavitation cycle. One relates to the cavitation collapse and t he other one corresponds to the cavitation shed off, both contributing to a distinctive stepwi se erosion damage growth pattern. Additional, more precise, simulations with much sho rter time step were performed to investigate the processes of cavitation collapse an d shedding off in more detail. There the importance of small cavitation structures which col lapse independently of the main cloud was Combined numerical and experimental investigation of the cavitation erosion process ___________________________________________________________________________________________ January 5 2015 Matevz Dular 2 found. The present work shows a great potential for future development of techniques for accurate predictions of cavitation erosion by numerical mean s o ly.